JPH04184453A - Coating liquid - Google Patents

Abstract

PURPOSE:To improve a preservable property by incorporating titanyl phthalocyanine having a peak at a specific Bragg angle in X-ray diffraction spectra and specific metal phthalocyanine having coordinate water or water of crystallization into the above coating liquid. CONSTITUTION:The phthalocyanine having the coordinate water or water of crystallization expressed by formula I is incorporated into the titanyl phthalocyanine having the peak at 27.2+ or -0.2 deg. of the Bragg angle 2theta of the charac teristic X-ray (1.541Angstrom ) of the CuKalpha ray in the X-ray spectra, more preferably the titanyl phthalocyanine dispersion having the peaks at 9.5+ or -0.2, 24.1+ or -0.2 deg. and 27.2+ or -0.2 deg. of the Bragg angle 2theta is incorporated into this coating liquid. In the formula I, M denotes a metal atom; X1 to X4 denote a hydrogen atom, etc. Y denotes a halogen atom; k, l, m, n denote 0 to 4 integer; p denotes 0 to 2 integer; q denotes >=1 integer. The ratio at which the metal phthalocyanine having the coordinate water or water of crystallization is incorporated into the titanyl phthalocyanine is preferably >=0.01% and <=20%. The preservable property is improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a coating liquid containing titanyl phthalonanine having a specific crystal type and a metal phthalocyanine having coordination water or water of crystallization.

[Prior art]

In recent years, research on photoconductive materials has been actively conducted, and they are being applied as photoelectric conversion elements such as electrophotographic photoreceptors, solar cells, and image sensors. Conventionally, inorganic materials have been mainly used as these photoconductive materials. For example, in electrophotographic photoreceptors, selenium,
Inorganic photoreceptors provided with a photosensitive layer mainly composed of an inorganic photoconductive material such as zinc oxide or cadmium sulfide have been widely used.

However, such inorganic photoreceptors do not always satisfy the characteristics such as photosensitivity, thermal stability, moisture resistance, and durability required of electrophotographic photoreceptors for copying machines and the like. For example, selenium crystallizes due to heat, fingerprint stains, etc., so its properties as an electrophotographic photoreceptor tend to deteriorate.

In addition, electrophotographic photoreceptors using cadmium sulfide are moisture resistant,
Durability is poor, and electrophotographic photoreceptors using zinc oxide also have durability problems.

Furthermore, in recent years, environmental issues have become particularly important, and selenium,
Due to the toxicity of cadmium sulfide electrophotographic photoreceptors,
The disadvantage is that there are severe restrictions on handling.

In order to improve the drawbacks of such inorganic photoconductive materials,
Various organic photoconductive substances have attracted attention, and attempts have been made to use them in photosensitive layers of electrophotographic photoreceptors, and active research has been conducted in recent years.

For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing polyvinyl rubazole trinitrofluorenone. However, this photoreceptor does not have sufficient sensitivity and durability. Therefore, a functionally separated electrophotographic photoreceptor has been developed in which the carrier generation function and the carrier transport function are assigned to different substances.

In such an electrophotographic photoreceptor, materials can be selected from a wide range, making it easy to obtain arbitrary characteristics, and it is therefore expected that an organic photoreceptor with excellent high sensitivity and high durability can be obtained.

Various organic compounds have been proposed as carrier-generating substances and carrier-transporting substances for such functionally separated electrophotographic photoreceptors. ing. Until now, the carrier-generating substance used was dibromoanthrone! = Photoconductive substances such as representative polycyclic quinone compounds, pyrylium compounds, eutectic complexes of pyrylium compounds, squareium compounds, phthalocyanine compounds, and azo compounds have been put into practical use. Furthermore, in general, the carrier-generating substance is applied by dispersing or dissolving it in an organic solvent. Therefore, in order to obtain a good electrophotographic photoreceptor, the carrier-generating substance must have good dispersibility and high dispersion stability. is required.

Furthermore, there is also a need for a carrier-generating material with high carrier-generating efficiency that provides higher sensitivity to electrophotographic photoreceptors. In this regard, in recent years, phthalocyanine compounds have attracted attention as excellent photoconductive materials, and active research is being conducted.

It is known that various physical properties of phthalocyanine compounds, such as spectra and photoconductivity, change depending on the type of central metal and crystal type. For example, copper phthalocyanine has σ, β, γ, and ε crystal types, and it has been reported that there are large differences in electrophotographic properties depending on these crystal types (Manabu Sawada, “Dye and "Drugs", 24 (6
), 122 (1979)).

In addition, especially in recent years, titanyl phthalocyanine has attracted attention, but titanyl 7-thalocyanine also has A, B, C,
Four main crystal forms called Y-forms have been reported.

However, type A described in JP-A No. 62-67094, type B described in JP-A 61-239248, and JP-A 62-2
Cm titanyl phthalocyanine of No. 56865' IR still has insufficient points in terms of electrophotographic sensitivity, durability, etc.

Recently announced Y-type titanyl phthalocyanine (Tree 1st grade,
Japan Hardcopy '89, E P 26
(1989)) is highly sensitive, but dispersion preparation techniques are important in order to fully utilize its properties and to produce it stably.

[Purpose of the invention]

An object of the present invention is to overcome the above-mentioned problems and provide a coating liquid with excellent durability and an electrophotographic photoreceptor coated with the coating liquid.

[Structure and effects of the invention]

The above object of the present invention is to
The Bragg angle 2θ of Ka line (wavelength 1.541) is 27.
Titanyl 7-thalocyanine having a peak at 2±0.2°, preferably a Bragg angle of 209.5±0.2°, 24.
This can be achieved by containing talocyanine having coordination water or crystal water represented by the following general formula CI) in a titanyl phthalocyanine dispersion having peaks at 1±0.2° and 27.2±0.2°. I can do it.

General formula (I) In the formula, M represents a metal atom, and X1 to X4 are a hydrogen atom, a halogen atom, or substituted or unsubstituted eight types of groups; an alkyl group, an aryl group, an alkoxy group, an aryloxy group. , represents an alkylthio group, an arylthio group, an amino group, or a heterocyclic group, and Y is a norogen atom, an oxygen atom, a hydroxyl group, substituted or unsubstituted five types of groups: an alkoxy group, an aryloxy group, an alkylthio group, Represents an arylthio group or a siloxy group. Furthermore, k, ρ, m, and n represent integers of θ to 4, p represents an integer of θ to 2, and q represents an integer of 1 or more.

The titanyl phthalocyanine used in the present invention is represented by the following general formula (II).

General formula (I[) However, X 1. X Z, X 3. X 4 represents a hydrogen atom, a hydrogen atom, an alkyl group, or an alkoxy group, and n, m, (2, and 2 represent integers from θ to 4).

The X-ray diffraction spectrum is measured under the following conditions, where a peak is a distinct sharp protrusion that is different from noise.

X-ray tube Cu voltage 40. OKV current 100 m A start angle
6. Odeg.

Stop angle 35.0 deg.

Step angle 0.02 deg.

Measurement time: 0-50 sec.

Although various methods can be used to synthesize titanyl phthalocyanine used in the present invention, it can typically be synthesized according to the following reaction formula (1) or (2).

r4 In the formula, R and -R represent a leaving group.

The titanyl phthalocyanine obtained as described above can be converted into the crystal form used in the present invention by performing the following treatment.

For example, any crystalline form of titanyl phthalocyanine is dissolved in concentrated sulfuric acid, the sulfuric acid solution is poured into water, and the precipitated crystals are collected by filtration. This operation converts titanyl phthalocyanine into an amorphous state.

Next, the crystal form used in the present invention can be obtained by treating this amorphous titanyl phthalocyanine with a specific organic solvent in the presence of water. However, the crystal conversion method is not limited to this method.

Next, the metal phthalocyanine given by the general formula CI) and used in the present invention has coordination water or water of crystallization. Examples of metal phthalocyanines include chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine,
Chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorosilicon phthalocyanine, dihydroxysilicon 7-polycyanine, dichlorogermanium 7-lyronoanine, dihydroxygermanium phthalocyanine, titanyl phthalocyanine, vanadyl phthalocyanine, thaloloindium phthalocyanine, dihydroxyindium phthalocyanine, dichlorozirconium phthalocyanine, dihydroxy Examples include zirconium phthalocyanine, dihydroxy/tin phthalocyanine, dihydroquine manganese phthalocyanine, copper phthalocyanine, iron phthalonanine, and the like.

Synthesis of these metal phthalonanines is achieved by known methods described in "Phthalocyanine Compounds" by Moser and Thomas, for example, by combining o-7 talonitrile or 1,3-diiminoisoindoline and a metal salt with σ-
It can be obtained by appropriately treating metal phthalocyanine obtained by reacting in an inert solvent such as talolnaphthalene.

There are several possible ways to incorporate metal phthalocyanine having coordination water or crystallization water into the specific crystal type titanyl phthalocyanine coating solution of the present invention. For example, each compound may be mixed in a solid state. Alternatively, metal phthalocyanine may be added to a dispersion of titanyl-7-talonanine. Alternatively, each phthalonanine may be once dissolved into a uniform state by acid paste treatment or the like to form a mixed crystal or complex, and then dispersed. Also, depending on the application, they may be contained in different layers, for example in the same device.

However, the method of containing it is not limited to these methods.

The ratio of metal phthalocyanine having coordination water or crystallization water to titanyl 7-lycyanine is usually 0.0001% or more and 100% or less, preferably 0.001% or more and 50% or less, and more preferably 0.0001% or more and 100% or less. 01
% or more and 20% or less.

The coating liquid of the present invention and the electrophotographic photoreceptor obtained by coating the coating liquid of the present invention may contain other photoconductive substances in addition to the above-mentioned phthalocyanine.

Other photoconductive substances include A, B, and C, which are different in crystal form from the titanyl 7-talonanine used in the present invention.
, amorphous, and AB mixed type titanyl phthalocyanine, other phthalocyanine compounds, naphthalocyanine compounds, other porphyrin derivatives, azo compounds, polycyclic quinone compounds represented by dibromoanthron, pyrylium compounds, and eutectic complexes of biryllium compounds. , squarium compounds, and the like.

Next, the electrophotographic photoreceptor obtained by coating the coating liquid of the present invention may be used in combination with a carrier transporting substance. Various carrier transport substances can be used, but representative examples include compounds having a nitrogen-containing heterocyclic nucleus and its condensed ring nucleus, such as oxazole, oxadiazole, thiazole, thiadiazole, imidazole, etc. Polyarylalkane compounds, pyrazoline compounds, hydrazone compounds, triarylamine compounds, styryl compounds, poly(bis)styryl compounds, styryltriphenylamine compounds, β-phenylstyryltriphenylamine compounds, Examples include butadiene compounds, hexatriene compounds, carbazole compounds, and fused polycyclic compounds.

Specific examples of these carrier transporting substances include carrier transporting substances described in JP-A-61-107356 and the like, and the structures of particularly typical ones are shown below.

(lO) ― 2Hs Various forms of the constituent layers of the photoreceptor are known.

Although the photoreceptor of the present invention can take any of these forms,
It is preferable to use a laminated or dispersed functionally separated photoreceptor. In this case, the configuration is usually as shown in FIGS. 1 to 6. Figure 1: The layer structure shown is that a carrier generation layer 2 is formed on a conductive support 1, and a carrier transport layer 3 is formed on this.
Figure 2 shows a photosensitive layer 4' formed by laminating these carrier generation layer 2 and carrier transport layer 3, and Figure 3 shows a photosensitive layer 4' formed by laminating the carrier generation layer 2 and carrier transport layer 3. An intermediate layer 5 is provided between the photosensitive layer 4 and the conductive support l having the layer structure shown in the figure. The layer structure in FIG. 5 is a carrier-generating substance 6.
A photosensitive layer 4'' containing a carrier transport material 7 and a carrier transport substance 7 is formed, and FIG. 6 shows an intermediate layer 5 provided between such a photosensitive layer 4'' and a conductive support 1. In the configurations shown in FIGS. 1 to 6, a protective layer can be further provided on the outermost layer.

In forming the photosensitive layer, it is effective to apply a solution in which a carrier-generating substance or a carrier-transporting substance is dissolved alone or together with a binder and an additive. However, the solubility of the carrier-generating substance is generally low, so in such cases, a liquid in which the carrier-generating substance is dispersed into fine particles in an appropriate dispersion medium using a dispersion device such as an ultrasonic dispersion machine, a ball mill, a sand mill, or a homomixer is used. The coating method is effective. In this case, the binder and additives are usually added to the dispersion.

A wide variety of solvents or dispersion media can be used to form the photosensitive layer.

For example, butylamine, ethylenediamine, N.

N-dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 4-methoxy-4-methyl-
2-pentanone, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, t-butyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, toluene, xylene,
Examples include acetophenone, chloroform, dichloromethane, dichloroethane, trichloroethane, methanol, ethanol, propatool, butanol, and the like.

When a binder is used to form the carrier generation layer or the carrier transport layer, any binder can be selected as the binder, and it is particularly desirable to use a hydrophobic polymer having film-forming ability. Examples of such polymers include, but are not limited to, the following:

Polycarboy-toPolycarpo-Z resinAcrylic resinMethacrylic resinPolyvinyl chloridePolyvinylidenePolystyreneStyrene-butadiene copolymerPolyvinyl acetatePolyvinyl formalPolyhinyl butyralPolyvinyl acecoolPolyvinylcarbazoleStyrene-alkyd resinLicone resinSilicone-alkyd resinSilicone - Butyral resin polyester polyurethane polyamide epoxy resin phenolic resin vinylidene chloride-acrylonitrile copolymer vinyl chloride-vinyl acetate copolymer vinyl chloride-vinyl acetate-maleic anhydride copolymer The ratio of carrier-generating substance to binder is 10 to 60
The content is preferably 0 wt%, and more preferably 50 to 400 wt%. The ratio of the carrier transport substance to the binder is preferably 10 to 500 wt%.

The thickness of the carrier generation layer is 0.01 to 20 μm, more preferably 0.05 to 5 μm. The thickness of the carrier transport layer is 1-100 μm, but more preferably 5-30 μm.
μm is preferred.

The photosensitive layer may contain an electron-accepting substance for the purpose of improving sensitivity, reducing residual potential, or reducing fatigue during repeated use. Examples of such electron-accepting substances include succinic anhydride, maleic anhydride, dibromo succinic anhydride, 7-thalic anhydride, tetrachlorophthalic anhydride, tetrabromo-7-thalic anhydride, 3-ditrophthalic anhydride, 4-
Nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene, 1
．． 3.5- Trinitrobenzene, p-nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, chloranil, dichlorodicyano-p-benzoquinone, anthraquinone, dinitroanthraquinone, 9
-Fluorenylidenemalonodinitrile, polynitro-9
~Fluorenylidene malonodinitrile, picric acid, 0
-Nitrobenzoic acid, p-nitrobenzoic acid, 3.5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3.5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity. can be mentioned.

The addition ratio of the electron-accepting substance is 1 weight of the carrier-generating substance.
00 to 0.01 to 200 is desirable;
．． 1 to 100 is preferred.

Further, the photosensitive layer may contain deterioration inhibitors such as antioxidants and light stabilizers for the purpose of improving storage stability, durability, and environmental dependence resistance. Compounds used for such purposes include, for example, chromanol derivatives such as tocopherol and their etherified or esterified compounds, polyarylalkane compounds, hydroquinone derivatives and their mono- and di-etherified compounds, benzophenone derivatives, and benzotriazole derivatives. conductors, thioether compounds, phosphonates, phosphorous esters,
Effective examples include phenylenediamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds, cyclic amine compounds, and hindered amine compounds. Specific examples of particularly effective compounds include rlRGANOX l
0IOJ, rlRGANOX 565J (manufactured by Ciba Geigy), [Sumilizer BHTJ, rThru-)ll
-Ilh11I++1 -Ilh11I++1 -Hindered amine compounds such as phenol compounds such as Sanol LS-2626J and Sanol LS-622LDJ (manufactured by Sankisha) are mentioned.

As the binder used for the intermediate layer, protective layer, etc., those listed above for the carrier generation layer and carrier transport layer can be used, but in addition, nylon resin, ethylene-vinyl acetate copolymer, ethylene-acetic acid Ethylene resins such as vinyl-maleic anhydride copolymers and ethylene-vinyl acetate-methacrylic acid copolymers, polyvinyl alcohol, cellulose derivatives, and the like are effective. Further, a hardening type binder using thermosetting or chemical hardening such as melamine, epoxy, isocyanate, etc. can be used.

Metal plates and metal drums are used as conductive supports, and thin layers of conductive polymers, conductive compounds such as indium oxide, or metals such as aluminum and palladium are coated, vapor-deposited, laminated, etc. A material provided on a base such as a plastic film can be used.

Furthermore, since the photoconductive composition obtained by applying the coating liquid of the present invention has a high photocarrier production efficiency, when used as an optical sensor or an optical recording material, it is possible to obtain one with extremely high sensitivity. can. Furthermore, when used as photovoltaic materials such as solar cells, it has high energy conversion efficiency.
You can get things.

When producing such an element, for example, a specific crystal type of titanyl phthalonanine of the present invention and a phthalocyanine having coordination water or crystal water are dispersed in an appropriate solvent,
A photoelectric conversion layer is formed by adding a binder, a carrier transport substance, a sensitizer, a durability improver, etc. as necessary and coating it on the electrode, and then an electrode layer is provided on top of that to form a photoelectric conversion cell. You can also do that. Or again,
It is also possible to use an element in which an n-type semiconductor layer or a p-type semiconductor layer is provided between the photoelectric conversion layer and the electrode, and a pn junction is formed between the photoelectric conversion layer and the photoelectric conversion layer.

Improved adhesion between each layer and between electrodes! Intermediate layers can be provided to improve the joint or joint area. Also, a photoelectric conversion layer for the purpose of improving conversion efficiency! : A method of providing adjacent carrier movement layers to prevent Keyliar recombination is also effective. Further, the dispersion medium, binder, carrier transport substance, electron-accepting compound, etc. used in producing the cell may be the same as those used in producing the electrophotographic photoreceptor.

〔Example〕

Example 1-1 1 part of titanyl phthalonanine and 0.01 part of chloroaluminum phthalonanine hydrate shown in FIG. 7 having a peak at 27.2° of the Bragg angle 2θ of the present invention! , and lincone resin (rKR-5240,1
1 part of 5% quintessence, butanol solution (manufactured by Shin-Etsu Chemical Co., Ltd.),
A dispersion liquid was obtained by dispersing 100 parts of methyl ethyl ketone as a dispersion medium using a sand mill.

This was applied onto a polyester base on which aluminum was vapor-deposited using a wire bar to form a carrier generation layer having a thickness of 0.2 μm.

Next, 1 part of carrier transport substance (1) and polycarboy
-T resin [Kneepilon Z200J (manufactured by Mitsubishi Gas Chemical Co., Ltd.)
1.3 parts and a trace amount of silicone oil rKF-54J (
A solution prepared by dissolving 1.2-dichloroethane (manufactured by Shin-Etsu Chemical Co., Ltd.) in 10 parts of 1,2-dichloroethane was coated using a blade coater, and after drying, a carrier transport layer having a thickness of 20 μm was formed. The photoreceptor thus obtained is referred to as sample 1.

Example 1-2 The dispersion obtained in Example kl was left in a dark place for one month at a temperature of 6000, and then a photoreceptor was prepared in the same manner as in Example 1-1. This will be referred to as sample 1'.

Example 2-1 A photoreceptor was prepared in exactly the same manner as in Example 1-1 except that hydroquinogallium phthalocyanine hydrate was used instead of chloroaluminum phthalocyanine hydrate. This is called sample 2.

Example 2-2 The dispersion obtained in “Example 2-” was prepared in the same manner as in Example 1-2.
After being left for a while, a photoreceptor was prepared. This is sample 2
'.

Example 3-1 A photoreceptor was prepared in the same manner as in Example 1-1 except that 0.05 part of chloroaluminum phthalonanine hydrate was used instead of 0.01 part in Example 1-1. . This is called sample 3.

Example 3-2 The dispersion obtained in Example 3-1 was prepared in the same manner as in Example 1-2.
After leaving it for a month, a photoreceptor was prepared.

This will be referred to as sample 3'.

Example 4-1 In Example 1-1, the titanyl phthalocyanine shown in FIG. 11 was used instead of the titanyl phthalocyanine shown in FIG. 7, and the carrier transport material (1) was used instead of the carrier transport material (1). A photoreceptor was prepared in exactly the same manner except that (22) was used.

This is called sample 4.

Example 4-2 The dispersion obtained in Example 4-1 was prepared in the same manner as in Example 1-2.
After leaving it for a month, a photoreceptor was prepared.

This will be referred to as sample 4'.

Comparative Example 1-1 A photoreceptor was prepared in exactly the same manner as in Example 1-1 except that chloroaluminum phthalocyanine hydrate was not used. This will be referred to as comparative sample (1).

Comparative Example 1-2 The dispersion obtained in Comparative Example 1-1 was prepared in the same manner as in Example 1-2.
After leaving it for a month, a photoreceptor was prepared.

This is referred to as a comparative example sample (1').

Evaluation 1 The samples obtained as described above were evaluated as follows using Paper Analyzer EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.). First, corona charging was performed for 5 seconds under the condition of -80 μA, and the surface potential Va immediately after charging and the surface potential Vi after being left for 5 seconds were determined.
(lux), and the surface potential is reduced to 1/2.
Exposure amount Ey required to make Vi, 1 surface potential 16
The exposure amount E6° required to lower the voltage from 00v to -100v. 7. . I asked for

Further, the dark decay rate was determined from the formula D=100(Va-Vi)/Va(%). The results are shown in Table 1.

From the above results, it was found that the coating liquid of the present invention exhibits excellent liquid storage stability.

Example 5 Vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslenc MF-IOJ" was placed on an aluminum drum.
(manufactured by Tanezu Kagaku Co., Ltd.) with a thickness of 0.1 μm was formed. On the other hand, 1 part of titanyl phthalocyanine and 0.01 part of hydroxyaluminum phthalocyanine hydrate as shown in FIG.

Dispersion was carried out by adding 35 parts of 2-dichloroethane.

To the obtained dispersion, 2 parts of carrier transport substance (1) was further added, and the mixture was coated on top of the intermediate layer by dip coating and dried to form a photosensitive layer with a thickness of 20 μm.

The photoreceptor thus obtained is designated as sample 5.

Further, the dispersion obtained in the same manner as in Example 1-2 was left to stand for one month, and then a photoreceptor was prepared in the same manner.

This will be referred to as sample 5'.

Photoreceptors were prepared in exactly the same manner as in Comparative Example 2 and Example 5, except that hydroxyaluminum phthalocyanine was not used. This is referred to as Comparative Sample (2), and the photoreceptor prepared after leaving this photoreceptor for one month is referred to as Comparative Sample (2').

The thus obtained sample was evaluated in the same manner as in Evaluation 1, except that the charging polarity was changed to positive polarity.

The results are shown in Table 2.

The coating liquid of the present invention also showed good liquid storage stability in the evaluation of positive charge.

Example 6 2 g of titanyl phthalo/anine shown in FIG.
5% xylene, butanol solution” Shin-Etsu Chemical IL) 30
g was dispersed using a sand mill in 50 mQ of 2-proper tool, and this was coated with a spinner onto a glass plate on which aluminum was vapor-deposited to give a thickness of 0.5μ, and a gold electrode was vapor-deposited thereon to form the present invention. cells were obtained.

The photoelectric conversion efficiency of the cell thus obtained was 1.7%.
showed a high value.

〔Effect of the invention〕

Since the coating liquid of the present invention exhibits excellent liquid storage properties, it can be stored for a long period of time without deteriorating the performance of the coating liquid.

Further, the electrophotographic photoreceptor obtained by coating the coating liquid of the present invention is stable in production and can maintain high sensitivity because the coating liquid does not deteriorate.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 to 1g6 are cross-sectional views showing specific examples of the layer structure of the photoreceptor of the present invention. 1... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4.4', 4''... Photosensitive layer 5... Intermediate layer FIGS. 7 to 11 are according to the present invention FIG. 2 is an X-ray diffraction spectrum diagram of titanyl phthalocyanine used for.

Claims (2)

[Claims] (1) In the X-ray diffraction spectrum, titanyl phthalocyanine has a peak at 27.2 ± 0.2° of the Bragg angle 2θ of CuKα rays (wavelength 1.541 Å) and the coordination represented by the following general formula [I] A coating liquid characterized by containing a metal phthalocyanine having water or water of crystallization. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, M represents a metal atom, and X_1 to X_4 are hydrogen atoms, halogen atoms, or substituted or unsubstituted 8 types of groups; alkyl groups , represents an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group or a heterocyclic group, and Y is a halogen atom, an oxygen atom, a hydroxyl group, a substituted or unsubstituted group of the following five types; an alkoxy group , represents an aryloxy group, an alkylthio group, an arylthio group, or a siloxy group. Moreover, k, l, m, and n represent integers of 0 to 4, p represents an integer of 0 to 2, and q represents an integer of 1 or more. ] (2) An electrophotographic photoreceptor obtained by coating the coating liquid according to claim 1.