JP3535618B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member.
For more information, see Visible
Photoreceptor sensitive to infrared and near infrared region
You. 2. Description of the Related Art Conventionally, in electrophotographic photosensitive members,
Inorganic photoconductor such as cadmium, zinc oxide, etc.
Having a photosensitive layer has been widely used
, But not always satisfactory in sensitivity, cost, printing durability, etc.
I couldn't do it. [0003] Organic feeling mainly composed of an organic photoconductive compound
Optics can be used for material design diversity, productivity, and economy.
And the fact that it is pollution-free and easy to handle
It has advantages and is currently undergoing active R & D.
You. In particular, charge generation and transport functions are shared among different substances
The function-separated type photoreceptor is currently
It is the mainstay. On the other hand, digital cameras such as laser printers have recently been used.
These organic photoconductors are used as photoconductors for recording
Use in the near-infrared light region corresponding to laser light (780 nm)
There is a growing demand for use, and high sensitivity characteristics in this area
The development of organic photoreceptors having the following is active. [0005] However, the conventional electronic photography
True photoreceptors are partially commercialized, but have high sensitivity and stability.
In terms of properties such as performance and life
There is no actual situation. Also, the emission range of the semiconductor laser
Of new photoconductors sensitive to long wavelengths
It is rare. The present invention has been made in view of the above.
Therefore, it is stable to heat and light and has a long wavelength range (near infrared range).
To provide a new electrophotographic photoreceptor with sufficient sensitivity
The task is to provide. The present inventor has solved the above-mentioned problems.
As a result of intensive research to solve this problem,
Electrophotographic photosensitive member having photosensitive layer containing charge generating substance
Titanyl phthalocyanine and hydrogen phthalate
Phthalocyan obtained by blending Russiannin in a specific ratio
Heat and light stable and long wavelength
With excellent photosensitivity even in the infrared region (near infrared region)
We found that a photoreceptor was obtained and completed the present invention.
Was. That is, the present invention provides a charge transport material and a charge generation material.
A photosensitive layer containing a biomaterial is provided on a conductive support.
In the photoconductor, the charge generating substance may be titanyl.
X is composed of phthalocyanine and hydrogen phthalocyanine.
Angle in the X-ray diffraction spectrum (2θ ± 0.2
゜) 6.8 ゜, 7.4 ゜, 15.0 ゜, 24.7 ゜, 2
With peaks at 6.2 °, 27.2 ° and 6.8 °
The ratio of the peak intensity of 27.2% to the peak intensity is 1 or more.
Characterized by containing a phthalocyanine mixed crystal as above
Electrophotographic photoreceptor. Embodiments of the present invention will be described below.
I do. <1> Phthalocyanine Mixed Crystal The photosensitive layer of the electrophotographic photoreceptor of the present invention comprises an electron-generating substance.
Hydrogen phthalocyanine (metal-free phthalocyanine)
Phthalo composed mainly of tanyl phthalocyanine
Contains a cyanine mixed crystal. The above hydrogen phthalocyanine and titanyl phthalate
The synthesis of Russiannin is based on Moser and Thomas' Phthalo
Cyanine compounds ”(MOSER and THOMAS,“ Phthalocianin
e Compounds ").
Alternatively, any other synthesis method may be used. For example, in the case of titanyl phthalocyanine,
heat melting o-phthalonitrile and titanium tetrachloride, or
Heat in the presence of an organic solvent such as α-chloronaphthalene
Method, 1,3-diiminoisoindoline and tetrabute
Xtitanium is added with an organic solvent such as N-methylpyrrolidone.
It can be obtained in good yield by heating. Hydrogen phthalocyanine
In the case of
You. In addition, the phthalocyanine-based compound thus synthesized
Has a hydrogen atom on the outer benzene ring replaced with chlorine, etc.
Chlorine-substituted phthalocyanine, etc.
No. A set of phthalocyanine mixed crystals used in the present invention
The formation of titanyl phthalocyanine and hydrogen phthalocyanine
Each mole fraction is preferably 95 to 40% and 5 to 60%.
But more preferably 95 to 50% and 5 to 50%, even more preferably
Preferably 95 to 60% and 5 to 40%, particularly preferably 9
0-60% and 10-40%. Titanyl phthalocyanine
If the mole fraction of nin is too high, the stability of the mixed crystal will decrease.
If it is too low, the sensitivity will decrease and it may not be practical.
There is. A method for producing a phthalocyanine mixed crystal is as follows.
For example, titanyl phthalocyanine and hydrogen phthalocyanine
Dissolving the acid in an acid and precipitating it with a mixture of water and an organic solvent
Method or method of precipitating the above acid solution with alcohol
Method, titanyl phthalocyanine and hydrogen phthalocyanine
Wet pace dissolved in acid and precipitated in water as above
A treatment with an organic solvent, and titanyl phthalo
In the presence of cyanine (or hydrogen phthalocyanine)
Synthesizes talocyanine (or titanyl phthalocyanine)
However, it is preferable to treat it with an organic solvent in the presence of water.
It is raised. The acid used in the above method is
Inorganic acids such as sulfuric acid and phosphoric acid, or methane sulfone
Acid, ethanesulfonic acid, fluoroacetic acid, chloroacetic acid, etc.
Organic acids, among which sulfuric acid, meta
Sulfonic acid and fluoroacetic acid are preferable, and further, sulfuric acid,
Methanesulfonic acid is more preferred. [0015] The amount of the acid used is titani as the raw material.
Amount to dissolve ruphthalocyanine and hydrogen phthalocyanine
There is no particular limitation as long as the raw material is phthalocyanine-based
Preferably 10 to 1000 g based on 1 g of the total amount of the compound
Is more preferable, and 50-500 g is more preferable. Ma
The temperature of the reaction system at the time of dissolution is -20 to 80 ° C.
Preferably, it is -10 to 30C. Melting temperature
If the temperature exceeds 80 ° C, the amount of the phthalocyanine-based compound
Solution may occur, and if it is lower than -20 ° C, solubility is poor.
It may be. As the alcohol used in the method
Is an aliphatic alcohol having 1 to 8 carbon atoms,
Aromatic alcohols, aromatic alcohols such as phenol, etc.
Is mentioned. Of these, methanol, ethanol,
Lopanol, butanol, pentanol, cyclopentane
And cyclohexanol, and methanol
, Ethanol, propanol, butanol, cyclohexane
Xanol is more preferably used. The phthalocyanine-based compound
To precipitate phthalocyanine mixed crystals from acid solutions
Mixed solution of water and organic solvent, alcohol,
Means that the amount of water is 5 per phthalocyanine compound acid solution.
１００100 times, preferably 5-20 times
Is more preferable. Deposition solvent for acid solution
If the amount is less than 5 times, it is difficult to control heat generation, and
If it is more than 0 times, operability may worsen as the amount increases.
is there. The deposition temperature in this case is -20 to 80 ° C.
Preferably, -10 to 40C is more preferable. An organic solvent used in the method of
For this purpose, one having a relative dielectric constant of 20 or less is used. Relative dielectric
When an organic solvent having a ratio exceeding 20 is used, the polarity is too high.
As a result, crystals that hinder performance will grow,
Mixed crystals cannot be obtained. With relative permittivity of 20 or less
Examples of the organic solvent include the following organic solvents.
Can be. In addition, in parentheses after each compound name,
2 shows the relative dielectric constant of the compound at 20 ° C. That is, carbon number 4-12, preferably charcoal
Aliphatic hydrocarbons having a prime number of 5 to 8 (1.7 to 2.0), charcoal
Alicyclic hydrocarbons having a prime number of 4 to 12, preferably 5 to 8 carbon atoms
Primates (2.0-2.5), benzene (2.3), tolue
(2.4), xylene (2.3-2.7), ethylbenzene
Aromatic hydrocarbons such as benzene (2.6), chloropentane
(6.6), butyl chloride (7.4), propyl chloride
(7.7), tetrachloroethane (2.3), dichloro
Ethane (10.7), carbon tetrachloride (2.2), chloropho
Lum (4.8), methylene chloride (7.8), butyl bromide
(7.1), propyl bromide (8.1), ethyl bromide
(9.4), halogenated fats such as methyl bromide (9.8)
Group hydrocarbons, chlorobenzene (5.7), dichlorobenzene
Benzene (2.4 to 9.9), bromobenzene (5.
4), halogens such as dibromobenzene (2.6 to 7.4)
Aromatic hydrocarbons, methyl ethyl ketone (18.
5), pentanone (15.4), hexanone (16.
4), methylcyclohexanone (14.0), cyclohexane
Xanone (18.3), dipropyl ketone (12.6)
Ketones, dibutyl ether (3.1), dihexy
Ether, ethylene glycol monomethyl ether
(16.0), ethylene glycol dimethyl ether
(5.5), tetrahydrofuran (7.4), dioxa
Ethers such as butane (2.2), methyl acetate (6.7),
Ethyl acetate (6.0), propyl acetate (6.0), acetic acid
Butyl (5.0), methyl propionate (5.5),
Ethyl lopionate (5.6), propyl propionate,
Butyl propionate (4.8), diethyl oxalate
(1.8), esters such as diethyl malonate (7.9)
, Ethylamine (7.0), dipropylamine (3.
1), butylamine (4.9), dibutylamine (3.
0), pentylamine, ethylhexylamine, cyclo
Hexylamine (4.7), dicyclohexylamine,
Aniline (7.1), toluidine (5.0-6.3),
Piperidine (5.8), pyridine (12.3), morph
And amines such as Colin (7.4). Of the above-mentioned organic solvents, in the present invention,
Toluene, xylene, chlorobenzene, dichlorobenzene
, Chloroform, methylene chloride, dichloroethane,
Trahydrofuran, dipropyl ketone, ethylamine,
Ethyl acetate and the like are preferably used, and further, toluene,
Chlorobenzene, dichlorobenzene, dichloroethane,
More preferably used are tetrahydrofuran, ethylamine and the like.
You can. Of water used in the above method and the above organic solvent.
The ratio of water in the combined liquid
Is preferably 5 to 90% by weight, and more preferably 20 to 90% by weight.
More preferably, it is 80% by weight. The organic solvent treatment in the method (1)
It is performed using a general stirrer, homomixer,
Int mixer, ball mill, sand mill, attritor
This can also be done using a computer, dispenser, ultrasonic disperser, etc.
Can be. The processing time is 1 minute to 120 hours, preferably.
Preferably 5 minutes to 50 hours, more preferably 10 minutes to 24 hours
The time range may be set. A lid obtained by any one of the above methods
The Russiannin mixed crystal was removed from the reaction solution by filtration.
It is isolated by drying and is
It is a raw material for the photosensitive layer of the body. Alternatively, the reaction solution
After isolating the talocyanine mixed crystal, solvent
Can be used as a coating solution for the photosensitive layer without going through the drying process
It is possible. The phthalocyanine mixed crystal used in the present invention
The body has a Bragg angle (2θ ±
0.2 ゜) 6.8 ゜, 7.4 ゜, 15.0 ゜, 24.7
5. peaks at {26.2}, 27.2}, and 6.
The peak intensity at 27.2 ° relative to the peak intensity at 8 °
The ratio of the peak strengths is 1 or more, and this ratio is more preferably
1 or more and 30 or less, more preferably 1 or more and 20 or less
You. 6.8 ゜ peak intensity in X-ray diffraction spectrum
Lid whose ratio of peak intensity to 27.2 ° is too large
The dark decay time tends to be shorter in Russiannin mixed crystals
Phthalocyanine mixed crystal whose ratio is less than 1.
May decrease the sensitivity and may not be suitable for practical use. Here, the X-ray diffraction spectrum in the present invention
Is measured by the powder method, and the measurement conditions are as follows.
is there. Target: Cu Kα ray divergence slit: 1 ゜ Scattering slit: 1 ゜ Receiving slit: 0.2 mm Step angle: 0.06 ゜ Counting time: 1 second <2> Electrophotographic photoconductor The electrophotographic photoconductor of the present invention is electrically conductive. Layer on photosensitive support
And the above-mentioned central substance as a charge generating substance together with a charge transporting substance
A phthalocyanine compound of two different qualities
It is characterized by containing at least one kind of thalocyanine mixed crystal.
And its physical configuration can be in any known form.
You may. That is, the electrophotographic photosensitive member of the present invention is
The main component is a phthalocyanine mixed crystal that is a load-generating substance
A charge generation layer and a charge transport layer mainly composed of a charge transport material.
Even when the laminated photosensitive layer is provided on a conductive support
Good and the charge generating material dispersed in the charge transport material
That the photosensitive layer is provided on a conductive support
You can also. In addition, a charging characteristic is provided between the conductive support and the photosensitive layer.
Polyamide resin, polyvinyl resin,
Organic polymers such as benzyl alcohol and cellulose,
It is also possible to provide an intermediate layer made of
You. As described above, the electrophotographic photosensitive member of the present invention
The photosensitive layer was formed on an electrically conductive support.
The thickness of the optical layer is preferably from 5 to 50 μm. Exposure
Function separation type of charge generation layer and charge transport layer used as layer
In this case, the charge generation layer preferably has a thickness of 0.001 to 10 μm.
m, more preferably 0.2 to 5 μm. charge
When the thickness of the generating layer is less than 0.001 μm, the layer is formed uniformly.
If it exceeds 10 μm, electrophotography
The characteristics tend to decrease. The thickness of the charge transport layer is
Preferably 5 to 50 μm, more preferably 8 to 20 μm
It is. If the thickness is less than 5 μm, the initial potential is low,
If it exceeds 50 μm, the sensitivity tends to decrease. In the electrophotographic photoreceptor of the present invention, the photoreceptor
Charge generation material contains the above phthalocyanine mixed crystal
However, in addition to this phthalocyanine mixed crystal,
Phthalocyanine compounds other than the above, azo pigments
It is also possible to use organic pigments that generate electric charges, etc.
is there. Further, in the photosensitive layer of the electrophotographic photosensitive member of the present invention,
Examples of the charge transport material used include, for example, trinitrofur
Negative charge transportability of olenone, tetranitrofluorenone, etc.
Electron-accepting substance, or, for example, poly-N-vinyl
Heterocyclic compounds such as carbazole
Polymer having chain, triazole derivative, oxadiazo
Derivatives, imidazole derivatives, pyrazoline derivatives,
Polyarylalkane derivatives, phenylenediamine derivatives
Body, hydrazone derivative, amino-substituted chalcone derivative,
Liarylamino derivatives, carbazole derivatives, stills
Positive charge transporting electron-donating substances such as ben derivatives
However, the charge transport material used in the present invention is
It is not limited to these. The photosensitive layer of the electrophotographic photosensitive member of the present invention is charged
When forming by mixing the generating substance and the charge transporting substance
Is a charge generating material containing the phthalocyanine mixed crystal
And the charge transport material are mixed in a weight ratio of 1:10 to 1: 2.
It is preferable that At this time, poly-N- is used as the charge transport material.
Having a heterocyclic compound such as vinyl carbazole in the side chain
When using a polymer, a binder resin can be used.
It is not necessary, but if other substances are used, binding
Agent resin is required. The amount of binder resin
30% by weight or more based on the total amount of the substance and the charge generating substance 5
It is preferably at most 00% by weight. Uses binder resin
If necessary, add a plasticizer and fluidity if necessary.
An additive, a pinhole inhibitor and the like can be added. This
When these additives are used, the amount of charge
5 times the total amount of the material, charge transport material and binder resin
It is preferable that the amount is not more than%. The photosensitive layer of the electrophotographic photosensitive member of the present invention is charged
A function-separable photosensitive layer consisting of a generating layer and a charge transport layer
In this case, the charge generation layer may serve as a charge generation material.
It contains a mixed crystal of Russiannin, but as described above,
It is also possible to contain an organic pigment that generates a load.
In addition, the charge generation layer includes a binder tree in addition to the charge generation substance.
Fats may be contained. In this case, the amount of binder resin
Is contained at 500% by weight or less based on the amount of the charge generating substance.
Preferably. In addition, the above-mentioned additives (plasticizer,
Fluidizing agents, pinhole inhibitors, etc.)
5% by weight or less based on the total amount of binder resin
May be. The charge transport layer is made of a charge transport material as described above.
It contains. For the charge transport layer, the binder resin is
Contains, for example, 500% by weight or less based on the amount of the substance
Can be done. In addition, the charge transport material is
In the case of materials, etc., the binder resin is
Is preferably contained in an amount of 50% by weight or more. In addition,
The above-mentioned additives may be charged-transported to the transport layer if necessary.
5% by weight or less based on the total amount of the sending substance and the binder resin
You may make it contain. As the binder resin, polycarbonate is used.
Polyester, methacrylic resin, acrylic resin,
Polyvinyl chloride, polyvinylidene chloride, polystyrene,
Rivinyl acetate, styrene-butadiene copolymer,
Vinylidene chloride-acrylonitrile copolymer, vinyl chloride
Vinyl acetate copolymer, vinyl chloride-vinyl acetate-none
Water maleic acid copolymer, silicone resin, silicon-Al
Kid resin, phenol-formaldehyde resin, styrene
Len-alkyd resin, poly-N-vinyl carbazole
, Polyvinyl butyral, fluororesin, urethane tree
Fat, alkyd resin, epoxy resin, melamine resin, etc.
Insulating resin, polyvinyl carbazole, polysila
And a semiconductive resin such as resin. In addition,
Thermosetting resin crosslinked by light and / or light and light curing
Water-soluble resins can also be used. As the electrophotographic photosensitive member of the present invention, for example,
A photosensitive layer containing a charge generating substance and a charge transporting substance
If used, the method of manufacture
Charge-generating substances containing talocyanine mixed crystals and charge transport
Add the substance, if necessary, in a suitable solvent with the binder resin.
Eh, in the usual way, for example, ball mills, attritors
ー, ultrasonic disperser, homomixer, paint mixer,
Dissolve uniformly with a kneading and dispersing machine such as a sand mill or disperser.
Dissolve or disperse, and apply the obtained photosensitive layer coating solution
Tur coater, blade coater, rod coater, recoater
Bath roll coater, spray coater, hot coater
, Squeeze coater, gravure coater, etc.
And apply it on a conductive support.
Drying is performed properly so that
And a method of forming a photosensitive layer. Also this place
Depending on the type of binder resin used,
After applying and drying, a curing reaction may be performed. As the solvent used for the photosensitive layer coating solution,
Dissolves charge generation material, charge transport material, binder resin, etc.
Limited if it can be solved or distributed
But not acetone, methyl ethyl ketone, cyclohexyl
Ketone-based solvents such as sanone, etc.
Aromatic solvents such as ter-based solvents, toluene, xylene, and salts
Halogenated hydrocarbon solutions such as methylene chloride and carbon tetrachloride
Agents, methanol, ethanol, propanol, etc.
Preferred solvents include a solvent-based solvent. Conductivity used for the electrophotographic photosensitive member of the present invention
Metallic plates, metal drums or conductive poly
Or conductive compounds such as indium oxide,
Conductive thin layer made of metal such as minium, palladium and gold
Paper, ceramic, etc. by means of coating, vapor deposition, lamination, etc.
Provided on substrates such as plastics, plastics and films
Is mentioned. These forms are sheet, drum,
Any form such as belt-shaped or seamless belt-shaped
Good. Further, the photosensitive layer of the electrophotographic photosensitive member generates electric charges.
Is a function-separated type consisting of a layer and a charge transport layer
The charge generation layer and the charge transport layer
The charge generation layer may be laminated on a conductive support.
The photosensitive layer may be sandwiched between the layers.
The method of forming on the support comprises:
The same as when using a substance containing a charge transport material
Method may be used. Hereinafter, the present invention will be described by way of examples. Sprout
In the following, a production example of a phthalocyanine mixed crystal used in the present invention will be described.
explain. Production Example 1 (Production of titanyl phthalocyanine) 1,3-diiminoy
58 g of indoline and 51 g of tetrabutoxytitanium are converted to α
-5 hours at 300C in 300 mL of chloronaphthalene
After the reaction, α-chloronaphthalene, dimethylformamide
Washing was performed in the order of (DMF). Then, hot DMF, hot water,
After washing with methanol and drying, 51 g of titanyl phthal
I got Anin. (Production of hydrogen phthalocyanine) 1,3-diiminoisoi
58 g of drin in 300 mL of α-chloronaphthalene
After reacting at 210 ° C. for 5 hours, α-chloronaphthalene, D
Washing was performed in the order of MF. Then, hot DMF, hot water, methano
And dried to obtain 42 g of hydrogen phthalocyanine.
Was. The titanyl phthalocyanate thus obtained
The following phthalocarbons are used as raw materials
A cyanine mixed crystal was produced. (Production example phthalocyanine mixed crystal) titanyl phthalocyanine
So that the mole fraction of the resin is 80%.
4 g of tanyl phthalocyanine and 0.9 of hydrogen phthalocyanine
g and 400 g of sulfuric acid cooled to 0 ° C.
The mixture was stirred at 0 ° C for 1 hour. The phthalocyanine is completely dissolved
After confirming that water was cooled to 0 ° C,
It was added to a mixture of 800 mL of ruene. Stir at room temperature for 2 hours
After stirring, the precipitated phthalocyanine mixed crystal was separated by filtration from the mixed solution.
Then, it was washed with methanol and water in that order. Check the neutrality of the wash water
After that, the phthalocyanine mixed crystal was separated from the washing water by filtration,
After drying, 4.4 g of a phthalocyanine mixed crystal was obtained. FIG. 1 shows the X-ray diffraction spectrum of this mixed crystal.
Show. Bragg angle (2θ ± 0.2 °) 6.8 °, 7.4
{, 15.0, 24.7, 26.2, 27.2}
And a peak intensity at 6.8 °
The ratio of the peak intensities at 27.2 ° is 5.2.
It turns out that it is the phthalocyanine mixed crystal of this invention. <X-ray diffraction measurement conditions> Model: JEOL JDX-3500 Target: Cu Kα tube voltage: 40 kV Tube current: 200 mA Divergence slit: 1 Scattering slit: 1 Light receiving slit: 0.2 mm Step angle: 0.06 mm Counting time: 1 second or less, all X-ray diffraction measurements were performed under the same conditions. For comparison, the following titanyl phthalo is used.
Manufactures cyanine crystals and comparative phthalocyanine mixed crystals
did. (Titanyl phthalocyanine crystal)
Except that 4 g of the obtained titanyl phthalocyanine was used.
The same treatment as in the production example of the phthalocyanine crystal was performed.
As a result, 3.1 g of titanyl phthalocyanine crystal was obtained. This
-Ray diffraction spectrum of titanyl phthalocyanine crystal
Is shown in FIG. Bragg angle (2θ ± 0.2 °) 7.3
{, 14.9}, 27.2}.
There is no peak at 8, 24.7 を, and 26.2 ゜.
It is different from the phthalocyanine mixed crystal of the invention. (Hydrogen phthalocyanine crystal) obtained above as raw material
Except that 4 g of hydrogen phthalocyanine was used.
The same treatment as in the production example of the cyanine mixed crystal was performed to
3.0 g of talocyanine crystal was obtained. This hydrogen phthalos
FIG. 3 shows the X-ray diffraction spectrum of the anine crystal. bra
13. Angle (2θ ± 0.2 °) 6.8 °, 7.4 °, 14.
Peaks at 9 °, 24.7 °, 26.2 °, but 2
The phthalocyanine of the present invention has no peak at 7.2 °
Different from mixed crystals. (Comparative Example Phthalocyanine Mixed Crystal) Titanyl Phthalocyanine
Titanyl phthalocyanine so that the mole fraction of
1.0g of Nin and 4.0g of hydrogen phthalocyanine as raw materials
Except for the molar fraction of the titanyl phthalocyanine
Exactly the same as in the production example of the phthalocyanine mixed crystal with a percentage of 80%
To obtain 4.3 g of a phthalocyanine mixed crystal.
Was. FIG. 4 shows the X-ray diffraction spectrum of this mixed crystal. B
Lag angle (2θ ± 0.2 °) 6.8 °, 7.4 °, 1
5.0 ゜, 24.7２６, 26.2 ゜, 27.2 ゜
The peak intensity at 6.8 °
The ratio of peak intensity at 7.2 ° is 0.5
Phthalocyanine mixed crystal. Note that the obtained chi
Phthalocyan with a molar fraction of tanyl phthalocyanine of 20%
The nin mixed crystal is hereinafter referred to as a comparative phthalocyanine mixed crystal. Production Example 2 The molar fraction of titanyl phthalocyanine is 80
%, So that the titanyl phthalocyanine obtained above becomes
4 g of hydrogen phthalocyanine 0.9 g and sulfuric acid 400 g
And completely dissolved at 0 ° C. Then add this acid solution to 2
The solution was dropped into 1500 mL of ethanol at 5 ° C,
Stirred for hours. Then, it is filtered and the filtrate is neutral with water.
Phthalocyanine mixed crystal
4.2 g were obtained. X-ray diffraction spectrum of this mixed crystal
It is shown in FIG. Bragg angle (2θ ± 0.2 °) 6.8 °,
7.4 ゜, 15.0 ゜, 24.7 ゜, 26.2 ゜, 2
Peak at 7.2 ° and peak at 6.8 °
The ratio of the peak intensity at 27.2 ° to the intensity is 5.
2 is the phthalocyanine mixed crystal of the present invention.
Call Production Example 3 The molar fraction of titanyl phthalocyanine was 70
%, So that the titanyl phthalocyanine obtained above becomes
3.5 g of hydrogen phthalocyanine and 1.3 g of hydrogen phthalocyanine
0 g and completely dissolved at 0 ° C. Then this acid solution
Into 800 mL of water and 2400 g of ice water.
After stirring for 1 hour at, this was filtered and the filtrate was
Washed until neutral. Jig this wet paste
Add to 300 mL of loroethane and stir at room temperature for 2 hours.
Was. Then filter and wash with water until the filtrate is neutral
Thus, 4.0 g of a phthalocyanine mixed crystal was obtained. This mixed crystal
X-ray diffraction spectrum of the sample is shown in FIG. Bragg angle (2θ
± 0.2 ゜) 6.8 ゜, 7.4 ゜, 15.0 ゜, 24.
With peaks at 7 °, 26.2 °, 27.2 °, and
At 27.2 ° relative to the peak intensity at 6.8 °
Phthalocyanine of the present invention having a peak intensity ratio of 3.5
It can be seen that this is a mixed crystal. Production Example 4 The molar fraction of titanyl phthalocyanine is 90
%, So that the titanyl phthalocyanine obtained above becomes
4.5 g of hydrogen phthalocyanine and 0.2 g of hydrogen phthalocyanine
0 g and completely dissolved at 0 ° C. Then this acid solution
Into 800 mL of water and 2400 g of ice water.
After stirring for 1 hour at, this was filtered and the filtrate was
Washed until neutral. Jig this wet paste
Add to 300 mL of loroethane and stir at room temperature for 2 hours.
Was. Then filter and wash with water until the filtrate is neutral
Thus, 4.2 g of a phthalocyanine mixed crystal was obtained. This mixed crystal
The X-ray diffraction spectrum of Bragg angle (2θ ± 0.2
゜) 6.8 ゜, 7.4 ゜, 15.0 ゜, 24.7 ゜, 2
With peaks at 6.2 °, 27.2 ° and at 6.8 °
Intensity at 27.2 ° relative to the peak intensity at
The degree ratio is 14 and the phthalocyanine mixed crystal of the present invention
You can see that there is. Examples 1 to 7 The phthalocyanines obtained in the above Production Examples
Using a mixed crystal as a charge generating substance,
Production example of aluminum plate with charge generation layer (conductive support)
Each of the phthalocyanine mixed crystals of No. 2 was prepared. 50 mg of phthalocyanine mixed crystal and polycarbonate
Bonate "Iupilon E-2000" (Mitsubishi Gas Chemical Company)
50 mg) and 2.5 mL of tetrahydrofuran.
And dispersed in a ball mill for 12 hours. This dispersion is
Apply on a plate so that the film thickness when dried is 1 μm.
After drying at 0 ° C., a charge generation layer was obtained. Next, the electric charge of the aluminum plate having the electric charge generating layer is described.
On the generating layer, p-diethylamino as a charge transport material
Benzaldehyde diphenylhydrazone or 2,5
-Bis (p-diethylaminophenyl) -1,3,4-
Using oxadiazole, the charge transport layer
And seven types of electrophotographic photosensitive members having the configurations shown in Table 1
Produced. 200 mg of charge transport material and polycarbonate
G Iupilon E-2000 (Mitsubishi Gas Chemical Company) 2
And dissolved in 2.5 mL of tetrahydrofuran.
The solution was applied so that the film thickness when dried was 15 μm,
It dried at 50 degreeC, and was set as the charge transport layer. Similarly, titanyl phthalocyanine crystal
Body, metal-free phthalocyanine crystal, comparative example phthalo
Preparation of electrophotographic photoreceptor of comparative example using cyanine mixed crystal
did. [Table 1] <Evaluation of Electrophotographic Photoreceptor of the Present Invention>
The evaluation of the electrophotographic characteristics of each of the obtained photoconductors was performed using a photoconductor evaluation device.
(Synthia-55, Gentec)
Was. First, the photosensitive member was rolled at a voltage of -6.0 kV.
Charge, hold in the dark for 1 second and measure the initial surface potential
After that, the xenon lamp light is separated using a monochromator.
Exposure with 780 nm monochromatic light, and an initial surface potential of 1
Measure the time to decay to / 2 and multiply by the incident light intensity
To sensitivity (E _1/2 (ΜJ / cm ^Two )). Table of results
1 is shown in the rightmost list. From these results, it was found that the electrophotographic photosensitive member of Comparative Example
E at 780 nm _1/2 Value is 1.8 or more.
As compared with the case where the degree is not good, 78
E at 0 nm _1/2 Is as small as 0.7 or less.
Is very good. The electrophotographic photoreceptor of the present invention has a thickness of 780 nm.
It has high sensitivity in the long wavelength range around
Excellent effect when used for user printer.
Also, a phthalocyanine mixed crystal used as a charge generating substance
However, since it is a crystal with good stability, durability and storage stability
It is possible to obtain an electrophotographic photoreceptor excellent in quality. Further
As a result, the coating liquid for the photosensitive layer of the electrophotographic photosensitive member
Storage stability is also improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing an X-ray diffraction spectrum of a phthalocyanine mixed crystal of Production Example 1. FIG. 2 is a view showing an X-ray diffraction spectrum of a titanyl phthalocyanine crystal. FIG. 3 is a view showing an X-ray diffraction spectrum of a hydrogen phthalocyanine crystal. FIG. 4 is a view showing an X-ray diffraction spectrum of a phthalocyanine mixed crystal of a comparative example. FIG. 5 is a view showing an X-ray diffraction spectrum of a phthalocyanine crystal of Production Example 2. FIG. 6 is a view showing an X-ray diffraction spectrum of a phthalocyanine mixed crystal of Production Example 3.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasuyuki Shigematsu 1000 Higashi-kuana-cho, Ushiku-shi, Ibaraki, Tsukuba Works, Mitsubishi Chemical Corporation (56) References JP-A-5-13387 (JP, A) JP-A-5-11471 (JP, A) JP-A-2-170167 (JP, A) JP-A-2-170166 (JP, A) JP-A-2-84662 (JP, A) A) JP-A-2-84661 (JP, A) JP-A-2-70763 (JP, A) JP-A-1-142658 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) G03G 5/00

Claims (1)

(57) [Claim 1] In an electrophotographic photosensitive member having a photosensitive layer containing a charge transporting substance and a charge generating substance provided on a conductive support, the charge generating substance is titanyl phthalocyanine. And hydrogen phthalocyanine, titanyl phthalocyanine
The molar fraction of each of nin and hydrogen phthalocyanine is 95-4.
0% and 5 to 60%, and in the X-ray diffraction spectrum, Bragg angles (2θ ± 0.2 °) 6.8 °, 7.4 °, 1
It has peaks at 5.0 °, 24.7 °, 26.2 °, 27.2 ° and 27.2 for a peak intensity of 6.8 °.
An electrophotographic photosensitive member comprising a phthalocyanine mixed crystal having a peak intensity ratio of 1 to 30 .