Electrophotographic photoreceptor

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to an electrophotographic photosensitive member using phthalocyanines as a charge generating substance and an enamine compound as a charge transporting substance on a conductive support.

【0002】

[Conventional technology]

In recent years, the use of electrophotographic methods has expanded not only to the field of copiers but also to fields where photographic technology has been used in the past, such as printing plates, slide films, and microfilms, and high speeds using lasers, LEDs, and CRTs as light sources. Application to printers is also being considered. Recently, applications of photoconducting materials other than electrophotographic photosensitive members, such as electrostatic recording elements, sensor materials, and EL elements, have begun to be studied. Therefore, the demands on photoconducting materials and electrophotographic photosensitive members using them are becoming more sophisticated and broader. Inorganic photoconducting substances such as selenium, cadmium sulfide, zinc oxide, and silicon have been known as electrophotographic photosensitive members, and have been widely studied and put into practical use. These inorganic substances have many advantages as well as various disadvantages. For example, selenium has the disadvantage that the production conditions are difficult and it is easy to crystallize due to heat or mechanical impact, and cadmium sulfide and zinc oxide have difficulty in moisture resistance and durability. It has been pointed out that silicon has insufficient chargeability and is difficult to manufacture. In addition, selenium and cadmium sulfide also have toxicity problems.

【0003】

On the other hand, organic photoconducting materials have good film-forming properties, excellent flexibility, light weight, good transparency, and design of photoconductors for a wide range of wavelengths by an appropriate sensitization method. Since it has advantages such as ease of use, its practical application is gradually attracting attention.

【0004】

By the way, the photoconductor used in electrophotographic technology is generally required to have the following basic properties. That is, (1) it is highly charged against corona discharge in a dark place, (2) the obtained charged charge is less leaked (dark attenuation) in a dark place, and (3) it is charged by light irradiation. Dissipation (light attenuation) is rapid, and (4) the residual charge after light irradiation is small.

【0005】

However, many studies have been conducted on photoconducting polymers such as polyvinylcarbazole as an organic photoconducting substance, but these are not necessarily sufficient in film property, flexibility, and adhesiveness, and are described above. It is hard to say that it has sufficient basic properties as a photoconductor.

【0006】

On the other hand, for organic low-molecular-weight photoconducting compounds, by selecting a binder or the like used for forming a photoconductor, a photoconductor having excellent mechanical strength such as filmability, adhesiveness, and flexibility can be obtained. However, it is difficult to find a suitable compound capable of retaining high-sensitivity properties.

【0007】

In order to improve such a point, an organic photoconductor having a higher sensitivity property has been developed by sharing the charge generation function and the charge transport function with different substances. The feature of such a photoconductor, which is called a function-separated type, is that a material suitable for each function can be selected from a wide range, and a photoconductor having arbitrary performance can be easily produced. Has been advanced.

【0008】

Of these, various substances such as phthalocyanine pigments, squarerium pigments, azo pigments, and perylene pigments have been studied as substances in charge of the charge generation function. Among them, azo pigments are capable of various molecular structures and are expensive. Since it can be expected to have charge generation efficiency, it has been widely studied and is being put to practical use. However, in this azo pigment, the relationship between the molecular structure and the charge generation efficiency has not yet been clarified. The reality is that we are searching for the optimum structure by accumulating a huge amount of synthetic research, but we are fully satisfied with the requirements such as the basic properties and high durability required for the photoconductors listed above. Things haven't been obtained yet.

【0009】

Further, in recent years, laser beam printers and the like, which use laser light as a light source instead of the conventional white light and have advantages of high speed, high image quality, and non-impact, have become widespread in combination with the progress of information processing systems. There is a demand for the development of materials that can withstand the demand. In particular, among laser beams, semiconductor lasers, whose application to compact discs and optical discs has increased in recent years and whose technological progress is remarkable, have been actively applied in the printer field as a compact and highly reliable light source material. In this case, since the wavelength of the light source is around 780 nm, it is strongly desired to develop a photoconductor having high sensitivity to long wavelength light of around 780 nm. Among them, the development of photoconductors using phthalocyanine, which has light absorption in the near infrared region, has been actively carried out. However, we have not yet obtained enough satisfaction.

【0010】

On the other hand, substances responsible for the charge transport function include hole transport substances and electron transport substances. Various substances such as hydrazone compounds and stilbene compounds as hole transporting substances, and 2,4,7-trinitro-9-fluorenone and diphenoquinone derivatives as electron transporting substances have been studied and are being put to practical use. The reality is that we are searching for the optimum structure by accumulating a huge amount of synthetic research. In fact, many improvements have been made so far, but none have yet been obtained that fully satisfy the requirements such as the basic properties and high durability required for the above-mentioned photoconductors.

【0011】

As described above, various improvements have been made in the production of electrophotographic photosensitive members, but those that fully satisfy the requirements such as the basic properties and high durability required for the above-mentioned photoconductors. Is not yet obtained.

【0012】

[Problems to be Solved by the Invention]

An object of the present invention is to provide an optimum electrophotographic photosensitive member capable of exhibiting high sensitivity and stable performance even after repeated use.

【0013】

[Means for solving problems]

The present inventors have reached the present invention as a result of conducting research to achieve the above object. That is, in the present invention, in an electrophotographic photosensitive member having a photosensitive layer containing a charge generating substance and a charge transporting substance on a conductive support, the charge generating substance is a phthalocyanine and the charge transporting substance is the following general formulas (1) and (2). ) Is at least one of the enamine compounds.

【0014】

[Chemical 2]

<img file="JPH1069107A_D0001.tif" />【0015】

In general formulas (1) and (2), R₁, R₂, R₄, R₅Represents an alkyl group, an aryl group, and a heterocycle which may have a substituent, respectively, and R₃, R₇Indicates a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxy group. n and m indicate integers from 0 to 2. Ar₁Indicates an alkyl group, an aralkyl group, an aryl group, or a heterocycle which may have a substituent. Ar₂, Ar₃, Ar₄, Ar₅Indicates a hydrogen atom, an aryl group which may have a substituent, and a heterocycle, respectively. Also, R₆Represents a group of atoms required to form a ring with a nitrogen atom.

【0016】

R₁, R₂, R₄, R₅Specific examples of the above include alkyl groups such as methyl group and ethyl group, aryl groups such as phenyl group and naphthyl group, and heterocycles such as furyl group and thienyl group. Also, R₁, R₂, R₄, R₅May have a substituent, and specific examples thereof include the above-mentioned alkoxy groups such as alkyl group, methoxy group and ethoxy group, and halogen atom such as fluorine atom and chlorine atom.

【0017】

Also, Ar₁Specific examples of the above include alkyl groups such as methyl group and ethyl group, aralkyl groups such as benzyl group and α-naphthylmethyl group, aryl groups such as phenyl group and naphthyl group, and heterocycles such as frill group and thienyl group. be able to. Also, Ar₁May have a substituent, and specific examples thereof include the above-mentioned alkoxy groups such as alkyl group, methoxy group and ethoxy group, and halogen atom such as fluorine atom and chlorine atom.

【0018】

Also, Ar₂, Ar₃, Ar₄, Ar₅Specific examples of the above include an aryl group such as a hydrogen atom, a phenyl group and a naphthyl group, and a heterocycle such as a frill group and a thienyl group. Also, Ar₂, Ar₃, Ar₄, Ar₅May have a substituent, and specific examples thereof include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a halogen atom such as a fluorine atom and a chlorine atom, and the above-mentioned aryl. The group can be mentioned.

【0019】

Also, R₃, R₇Specific examples of the above include alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, and halogen atoms such as fluorine atom and chlorine atom. Also, R₃, R₇May have a substituent, and examples thereof include the above-mentioned alkyl group and the above-mentioned halogen atom.

【0020】

Also, R₆, And specific examples of the ring formed from the nitrogen atom and the like include a carbazole ring, a phenothiazine ring, a phenothiazine ring, a tetrahydroquinoline ring and the like. Also, R₆, And the ring formed from a nitrogen atom or the like may have a substituent, and specific examples thereof include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, fluorine and chlorine. Halogen atoms such as, etc. can be mentioned.

【0021】

BEST MODE FOR CARRYING OUT THE INVENTION

Specific examples of the charge transporting substances represented by the general formulas (1) and (2) according to the present invention include, for example, those having the structural formulas shown in the following A-01 to 47, but are limited thereto. It's not a thing.

【0022】

[Chemical 3]

<img file="JPH1069107A_D0002.tif" />【0023】

[Chemical 4]

<img file="JPH1069107A_D0003.tif" />【0024】

[Chemical 5]

<img file="JPH1069107A_D0004.tif" />【0025】

[Chemical 6]

<img file="JPH1069107A_D0005.tif" />【0026】

[Chemical 7]

<img file="JPH1069107A_D0006.tif" />【0027】

[Chemical 8]

<img file="JPH1069107A_D0007.tif" />【0028】

[Chemical 9]

<img file="JPH1069107A_D0008.tif" />【0029】

[Chemical 10]

<img file="JPH1069107A_D0009.tif" />【0030】

[Chemical 11]

<img file="JPH1069107A_D0010.tif" />【0031】

As the phthalocyanines used in the present invention, any of phthalocyanines known per se and derivatives thereof can be used. Specifically, metal-free phthalocyanines, titanyloxyphthalocyanines, copper phthalocyanines, aluminum phthalocyanines, diphenoxygermanium. Phthalocyanines, germanium phthalocyanines, gallium phthalocyanines, chlorogallium phthalocyanines, bromogallium phthalocyanines, chloroindium phthalocyanines, bromoindium phthalocyanines, iododium phthalocyanines, magnesium phthalocyanines, chloroaluminum phthalocyanines, bromoaluminum phthalocyanines, Suzuphthalocyanines, dichlorostinphthalocyanines, vanadyloxyphthalocyanines, zinc phthalocyanines, cobalt phthalocyanines, nickel phthalocyanines, hydroxygallium phthalocyanines, dihydroxygallium phthalocyanines, barium phthalocyanines, beryllium phthalocyanines, cadmium phthalocyanines, chlorocobalt Examples thereof include phthalocyanines, dichlorotitanyl phthalocyanines, iron phthalocyanines, silicon phthalocyanines, lead phthalocyanines, platinum phthalocyanines, metal-free naphthalocyanines, aluminum naphthalocyanines, titanyloxynaphthalocyanines, ruthenium phthalocyanines, palladium phthalocyanines and the like. .. In particular, among them, metal-free phthalocyanine, titanyloxyphthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, diphenoxygermanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferably used in the present invention.

【0032】

Further, phthalocyanines are known as crystalline polymorphic compounds, and various crystalline phthalocyanines have been found. As a description of these crystal types and manufacturing methods, metal-free phthalocyanines are described in JP-A-49-4338, JP-A-58-182639, JP-A-60-19151, and JP-A-62-47054. , Japanese Patent Application Laid-Open No. 62-143058, Japanese Patent Application Laid-Open No. 63-286857, Japanese Patent Application Laid-Open No. 1-138563, Japanese Patent Application Laid-Open No. 1-230581, Japanese Patent Application Laid-Open No. 2-233769, and J. Phys. Chem .72, It has been. Chloroaluminum phthalocyanines can be found in JP-A-58-158649, JP-A-62-133462, JP-A-62-163060, JP-A-63-43155, and JP-A-64-70762. In Japanese publications, chloroindium phthalocyanine is described in JP-A-59-44054, JP-A-60-59355, JP-A-61-45249, and further in JP-A-7-133375. In JP-A-63-18361, JP-A-1-204968, JP-A-268763, JP-A-3-269063, and JP-A-7-247442, diphenoxyphthalocyanine is described in JP-A-4. -360150, chlorogallium phthalocyanine, JP-A-5-194523, further, JP-A-7-102183, hydroxygallium phthalocyanine, JP-A-5-263007, and JP-A-7-53892. Examples thereof include those described in the publication.

【0033】

In the present invention, those having the following Bragg angle (2θ ± 0.2 °) with respect to X-rays of CuKα1.541 ongstrom are particularly preferably used. Metal-free phthalocyanine Metallic phthalocyanine (τ-type metalless phthalocyanine), 7.5 °, 9.1 °, 16.8 °, 17.3 with X-ray diffraction spectra showing major peaks at 7.6 °, 9.2 °, 16.8 °, 17.4 °, 20.4 °, 20.9 ° Metallic phthalocyanine (τ'-metalless phthalocyanine) with X-ray diffraction spectra showing major peaks at °, 20.3 °, 20.8 °, 21.4 °, 27.4 °, 7.6 °, 9.2 °, 16.8 °, 17.4 °, 28.5 Metal-free phthalocyanine (η-type metal-free phthalocyanine), 7.5 °, 9.1 °, 16.8 °, 17.3 ° with X-ray diffraction spectra showing major peaks at ° or 7.6 °, 9.2 °, 16.8 °, 17.4 °, 21.5 ° , 20.3 °, 20.8 °, 21.4 °, 27.4 ° or 7.5 °, 9.1 °, 16.8 °, 17.3 °, 20.3 °, 20.8 °, 21.4 °, 22.1 °, 27.4 °, 28.5 ° X showing major peaks Metal-free phthalocyanine with line diffraction spectrum (η'type metal-free phthalocyanine), metal-free phthalocyanine with X-ray diffraction spectrum showing major peaks at 7.7 °, 9.3 °, 16.9 °, 22.4 °, 28.8 °, at 6.7 ° Metallic phthalocyanine having an X-ray diffraction spectrum showing the main peak, metal-free phthalocyanine having an X-ray diffraction spectrum showing a shoulder at 13.5 ° around 15.2 °, X-ray diffraction showing a shoulder at 24.8 ° around 26.8 ° Metallic phthalocyanine with spectrum, 6.7 °, 8.7 °, 15.1 °, 17.7 °, 23.8 °, 26.1 °, 27.4 °, 30.0 ° Metallic phthalocyanine with X-ray diffraction spectrum showing major peaks, 6.7 °, 7.2 Metallic phthalocyanine with X-ray diffraction spectra showing major peaks at °, 13.4 °, 14.5 °, 15.2 °, 16.0 °, 20.2 °, 21.7 °, 24.0 °, 24.8 °, 24.8 °, 26.6 °, 27.3 °, 6.6 °, 13.4 °, 14.5 °, 20.2 °, 24.8 °, 26.6 °, 27.Metallic phthalocyanine with X-ray diffraction spectrum showing the main peak at 2 °, X-ray spectrum showing the main peak at 6.7 °, 7.3 °, 13.5 °, 14.9 °, 15.9 °, 16.7 ° 24.7 °, 26.1 ° Metallic phthalocyanines with, or metalless phthalocyanines with X-ray diffraction spectra showing major peaks at 7.4 °, 9.0 °, 16.5 °, 17.2 °, 22.1 °, 23.8 °, 27.0 °, 28.4 °.

【0034】

Titanyloxyphthalocyanine Titanyloxyphthalocyanine (α-type titanyloxyphthalocyanine), 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7, which has an X-ray diffraction spectrum showing major peaks at 7.5 °, 12.3 °, 16.3 °, 25.3 °, and 28.7 °. Titanyloxyphthalocyanine (β-type titanyloxyphthalocyanine), 7.0 °, 15.6 °, 23.4 °, 25.5 ° with X-ray diffraction spectra showing major peaks at °, 16.1 °, 20.8 °, 23.3 °, 26.3 °, 27.1 ° Titanyloxyphthalocyanine (C-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing a major peak in, and titanyloxyphthalocyanine (m-type titanyl) having an X-ray diffraction spectrum showing a major peak at 6.9 °, 15.5 °, and 23.4 °. Oxyphthalocyanine), 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 °, 27.3 ° (Y-type titanyloxyphthalocyanine) with X-ray diffraction spectra showing major peaks Titanyloxyphthalocyanine, 7.3 °, Titanyloxyphthalocyanine (γ-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 17.7 °, 24.0 °, 27.2 °, and 28.6 °, with major peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 °. Titanyloxyphthalocyanine having the X-ray diffraction spectrum shown (type I titanyloxyphthalocyanine), titanyloxyphthalocyanine having the X-ray diffraction spectrum showing the main peaks at 7.4 °, 10.1 °, 12.4 °, 24.1 °, 25.2 °, 28.5 ° (Ω-type titanyloxyphthalocyanine), titanyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 7.4 °, 11.0 °, 17.9 °, 20.1 °, 26.5 °, 29.0 ° (E-type titanyloxyphthalocyanine), 7.5 ° , 22.4 °, 24.4 °, 25.4 °, 26.2 °, 27.2 °, 28.Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 6 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 9.2 °, 13.1 °, 20.7 °, 26.2 °, 27.1 °, 7.3 ° , Titanyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 22.9 ° and 27.4 °, 7.6 °, 10.5 °, 12.5 °, 15.6 °, 16.4 °, 17.7 °, 26.3 °, 28.9 °, 30.5 °, 32.0 Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 26.2 °, X showing a major peak at 7.3 °, 15.2 °, 26.2 ° Titanyloxyphthalocyanine with line diffraction spectrum, titanyloxyphthalocyanine with X-ray diffraction spectrum showing major peaks at 13.1 °, 20.6 °, 26.1 °, 27.0 °, 6.7 °, 7.4 °, 10.2 °, 12.6 °, 15.2 ° , 16.0 °, 17.1 °, 18.2 °, 22.4 °, 23.2 °, 24.2 °, 25.2 °, 28.5 °, titanyloxyphthalocyanine with X-ray diffraction spectrum showing the main peak, X-ray showing the main peak at 27.3 ° Titanyloxyphthalocyanine with diffraction spectrum, major peaks at 6.8 ° and 27.3 ° Titanyloxyphthalocyanine with X-ray diffraction spectrum, major peaks at 7.4 °, 11.0 °, 17.9 °, 20.1 °, 26.4 ° and 29.0 ° Titanyl oxyphthalocyanine having an X-ray diffraction spectrum showing, 9.2 °, 11.6 °, 13.0 °, 24.1 °, 26.2 ° having a titanyl oxyphthalocyanine showing a major peak at 6.8 °, 9.7 °, 15.4 °. , Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.2 °, 9.1 °, 12.2 °, 16.3 °, 26.Titanyloxyphthalocyanine with X-ray diffraction spectrum showing the main peak at 9 °, 7.4 °, 9.2 °, 10.4 °, 11.6 °, 13.0 °, 14.3 °, 15.0 °, 15.5 °, 23.4 °, 24.1 °, 26.2 ° , Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.2 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 9.5 °, 24.1 °, 27.2 °, 7.2 °, 14.2 °, 24.0 Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at °, 27.2 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 4.8 °, 9.6 °, 26.2 °, 6.5 °, 14.5 °, Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 23.8 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.0 °, 9.1 °, 14.1 °, 26.2 °, 6.8 °, 14.9 ° , Titanyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 24.8 ° and 26.2 °, Titanyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 7.5 ° and 27.3 °, mainly at 21.6 ° and 28.0 ° Titanyloxyphthalocyanine having an X-ray diffraction spectrum of, Titanyloxyphthalocyanine having a major X-ray diffraction spectrum at 9.6 ° and 27.2 °, an X-ray diffraction spectrum showing major peaks at 7.3 °, 19.4 °, 21.5 ° and 23.8 ° Titanyloxyphthalocyanine having X-ray diffraction spectra showing major peaks at 10.5 °, 12.6 °, 15.0 °, 26.6 °, 8.5 °, 13.6 °, 17.1 °, 18.0 °, 23.9 °, 27.4 ° Titanyloxyphthalocyanine, which has an X-ray diffraction spectrum showing major peaks in, 8.9 °, 11.4 °, 27.Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 2 ° 7.5 °, 22.5 °, Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 28.6 °, 6.8 °, 26.1 °, 27.1 ° Titanyloxyphthalocyanine with an X-ray diffraction spectrum showing the main peak, titanyloxyphthalocyanine with an X-ray diffraction spectrum showing the main peak at 8.4 °, 7.6 °, 10.3 °, 12.7 °, 16.3 °, 22.7 °, Titanyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 24.3 °, 25.5 ° and 28.6 °, X-ray diffraction showing major peaks at 6.8 °, 7.4 °, 15.0 °, 24.7 °, 26.2 ° and 27.2 ° Titanyl oxyphthalocyanine having a spectrum, or titanyl oxyphthalocyanine which is an amorphous form having no clear peak.

【0035】

Copper phthalocyanine Copper phthalocyanine (β-type copper phthalocyanine), which has an X-ray diffraction spectrum showing major peaks at 7.0 °, 9.2 °, 12.5 °, 16.8 °, 18.6 °, 21.3 °, 23.8 °, 26.2 °, 28.0 °, 30.5 °, Copper phthalocyanine (ε-type copper phthalocyanine), which has an X-ray diffraction spectrum showing major peaks at 7.6 °, 9.1 °, 14.2 °, 17.4 °, 20.4 °, 21.2 °, 23.0 °, 26.5 °, 27.2 °, 29.5 °, Copper phthalocyanine (α-type copper phthalocyanine) having an X-ray diffraction spectrum showing major peaks at 7.0 °, 9.8 °, 15.8 °, 24.9 °, 26.7 ° and 27.3 °, major peaks at 7.0 °, 7.7 ° and 9.2 ° Copper phthalocyanine having an X-ray diffraction spectrum showing.

【0036】

Chloroaluminum phthalocyanine Chloroaluminum phthalocyanine with an X-ray diffraction spectrum showing a major peak at 7.0 °, chloroaluminum phthalocyanine with an X-ray diffraction spectrum showing a major peak at 6.7 °, 11.2 °, 16.7 °, 25.6 °, major at 25.5 ° Chloroaluminum phthalocyanine with X-ray diffraction spectra showing peaks or chloro with X-ray diffraction spectra showing major peaks at 6.5 °, 11.1 °, 13.7 °, 17.0 °, 22.0 °, 23.0 °, 24.1 °, 25.7 ° Aluminum phthalocyanine.

【0037】

Chloroindium phthalocyanine Chloroindium phthalocyanine with an X-ray diffraction spectrum showing major peaks at 7.4 °, 16.7 ° and 27.8 °.

【0038】

Vanadyl oxyphthalocyanine Vanadyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 9.3 °, 10.7 °, 13.1 °, 15.1 °, 15.7 °, 16.1 °, 20.7 °, 23.3 °, 26.2 °, 27.1 °, 7.5 °, 24.2 ° Vanadyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 27.7 ° and 28.6 °, vanadyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at 14.3 °, 18.0 °, 24.1 ° and 27.3 °, 7.4 Vanadyloxyphthalocyanine with X-ray diffraction spectra showing major peaks at °, 10.3 °, 12.6 °, 16.3 °, 17.8 °, 18.5 °, 22.4 °, 24.2 °, 25.4 °, 27.2 °, 28.6 °, or distinct Vanadyl oxyphthalocyanine which is an amorphous type having no peak.

【0039】

Chlorogallium phthalocyanine Chlorogallium phthalocyanine with X-ray diffraction spectra showing major peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 °, chlorogallium phthalocyanine with X-ray diffraction spectra showing major peaks at 11.0 °, 13.5 ° and 27.1 ° Chlorogallium phthalocyanine with X-ray diffraction spectra showing major peaks at 6.8 °, 17.3 °, 23.6 °, 26.9 °, or X-rays showing major peaks at 8.7-9.2 °, 17.6 °, 27.4 °, 28.8 ° Chlorogallium phthalocyanine having a diffraction spectrum.

【0040】

Hydroxy gallium phthalocyanine Hydroxygallium phthalocyanines with X-ray diffraction spectra showing major peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 28.3 °, major at 7.7 °, 16.5 °, 25.1 °, 26.6 ° Hydroxygallium phthalocyanine with X-ray diffraction spectra showing peaks, hydroxygallium phthalocyanines with X-ray diffraction spectra showing major peaks at 7.9 °, 16.5 °, 24.4 °, 27.6 °, 7.0 °, 7.5 °, 10.5 °, 11.7 Hydroxygallium phthalocyanine with X-ray diffraction spectra showing major peaks at °, 12.7 °, 17.3 °, 18.1 °, 24.5 °, 26.2 °, 27.1 °, major peaks at 6.8 °, 12.8 °, 15.8 °, 26.0 ° Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing, or hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 7.4 °, 9.9 °, 25.0 °, 26.2 °, 28.2 °.

【0041】

Diphenoxy germanium phthalocyanine Diphenoxygermanium phthalocyanine with X-ray diffraction spectra showing major peaks at 9.0 °, 11.2 °, 17.1 °, 18.1 °, 20.9 °, 22.7 °, 25.8 °, 29.3 °.

【0042】

Generally, phthalocyanine is produced by the phthalocyanine method in which phthalocyanine and a metal chloride or an alkoxy metal are heated and melted or heated in the presence of an organic solvent, and phthalic anhydride is heated and melted with urea and a metal chloride. Alternatively, there are a Wyler method of heating in the presence of an organic solvent, a method of reacting cyanobenzamide with a metal salt at a high temperature, a method of reacting dilithium phthalocyanine with a metal salt, and the like, but the method is not limited thereto. The organic solvents used in the reaction include α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, diphenylnaphthalene, ethylene glycol, dialkyl ether, quinoline, sulfolane, dichlorobenzene, and N-methyl-2-. A reaction-inactive high-boiling solvent such as pyrrolidone or dichlorotoluene is desirable.

【0043】

The phthalocyanine compound obtained by the above method can be used as an acid, alkali, acetone, methanol, ethanol, methyl ethyl ketone, tetrahydrofuran, pyridine, quinoline, sulfolane, α-chloronaphthalene, toluene, xylene, dioxane, chloroform, dichloroethane, N, N'-. Purification with dimethylformamide, N-methyl-2-pyrrolidone, etc. provides a high-purity phthalocyanine compound that can be used for electrophotographic applications. Examples of the purification method include a washing method, a recrystallization method, an extraction method such as Soxhlet, a heat suspension method, and a sublimation method. Further, the purification method is not limited to these, and any operation may be used as long as it is an operation of removing unreacted products and reaction by-products.

【0044】

Next, a synthesis example in the present invention will be described in more detail, but the present invention is not limited thereto.

【0045】

Synthesis example 1 Synthesis of titanyloxyphthalocyanine (β type) Dissolve 25.5 g of 1,3-diiminoisoindoline and 15.0 g of titanium tetra-n-butoxide in 180 ml of 1-chloronaphthalene, and heat and stir at 180 ° C on an oil bath. After 5 hours, the precipitated crystals were collected by filtration, washed successively with toluene and acetone, and dried to obtain 21.4 g of titanyloxyphthalocyanine crystals. The IR spectrum of this compound is shown in FIG. 1 and the X-ray diffraction spectrum is shown in FIG.

【0046】

Synthesis example 2 Synthesis of titanyloxyphthalocyanine (amorphous) 3.0 g of titanyloxyphthalocyanine obtained in Synthesis Example 1 was slowly added to 150 ml of concentrated sulfuric acid cooled to about 0 ° C to dissolve it. This solution was slowly poured into 1.2 liters of chilled ice water to precipitate crystals. The crystals were collected by filtration, washed with water until neutral, and dried to obtain 2.6 g of amorphous titanyl phthalocyanine. The IR spectrum of this compound shows the same peak as in FIG. 2, and the X-ray diffraction spectrum is shown in FIG. From these, it was confirmed that only the crystal form was converted by this operation without decomposing the compound.

【0047】

Synthesis example 3 Synthesis of titanyloxyphthalocyanine (Y type) The amorphous titanyl phthalocyanine (2.0 g), water (28.0 g) and chlorobenzene (6.0 g) obtained in Synthesis Example 2 were heated and stirred at 50 ° C. After 1 hour, the mixture was cooled to room temperature, the crystals were collected by filtration, and washed with methanol. Drying gave 1.7 g of Y-type titanyl phthalocyanine. The X-ray diffraction spectrum of this compound is shown in FIG.

【0048】

Hereinafter, phthalocyanines synthesized by the same method and their X-ray diffraction spectra are shown. m-type titanyloxyphthalocyanine (Fig. 5), diphenoxygermanium phthalocyanine (Fig. 6).

【0049】

[Chemical 12]

<img file="JPH1069107A_D0011.tif" />【0050】

Synthesis Example 4 Synthesis of Exemplified Compound A-10 Dissolve 3.35 g of diethylbenzohydrylphosphonate and 2.51 g of the aldehyde compound (3) shown above in 20 ml of N, N'-dimethylformamide (DMF), and slowly add 1.68 g of potassium t-butoxide under stirring at room temperature. It was. After 1 hour, the reaction solution was poured into 300 ml of water and 200 ml of ethyl acetate, and the organic layer was separated. The mixture was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 2.3 g of Exemplified Compound A-10. Melting point 85.0 ~ 88.0 ° C.

【0051】

[Chemical 13]

<img file="JPH1069107A_D0012.tif" />【0052】

Synthesis Example 5 Synthesis of Exemplified Compound A-14 3.04 g of 4-chloromethylbiphenyl and 2.50 g of triethylphosphite were heated and stirred at 140 ° C. After 7 hours, the mixture was cooled to room temperature, and 3.75 g of the aldehyde compound (4) shown above and 70 ml of DMF were added. Under stirring at room temperature, 3.93 g of sodium methylate (28%, methanol solution) was added dropwise, and stirring was continued at the same temperature for 1 hour. Then, the reaction solution was poured into 400 ml of ice water to precipitate crystals. The crystals were collected by filtration through a glass filter and washed with water and isopropyl alcohol. The obtained crude crystals were recrystallized from methyl cellosolve to obtain Exemplified Compound A-14. Melting point 162.4 ~ 163.6 ° C.

【0053】

Synthesis Example 6 Synthesis of Exemplified Compound A-15 2.57 g of cinnamyl bromide and 2.17 g of triethylphosphite were heated and stirred at 120 ° C. After 5 hours, the reaction mixture was cooled to room temperature and distilled under reduced pressure to obtain 2.38 g of triethyl cinnamylphosphonate. 2.28 g of triethyl cinnamylphosphonate obtained as described above and 2.81 g of the aldehyde compound (4) shown above were dissolved in 35 ml of DMF, and 2.18 g (28%, methanol solution) of sodium methylate was added dropwise at room temperature with stirring. After 1 hour, the reaction solution was poured into 300 ml of ice water to precipitate crystals. The crystals were collected by filtration through a glass filter and washed with water and ethanol. The obtained crude crystals were recrystallized from methyl cellosolve to obtain 2.95 g of Exemplified Compound A-15. Melting point 156.0 ~ 157.1 ° C.

【0054】

[Chemical 14]

<img file="JPH1069107A_D0013.tif" />【0055】

Synthesis Example 7 Synthesis of Exemplified Compound A-41 3.34 g of diethyl benzhydrylphosphonate and 2.49 g of the aldehyde compound (5) shown above were dissolved in 15 ml of DMF, and 2.24 g of potassium t-butoxide was slowly added under stirring at room temperature. After 3 hours, the reaction solution was poured into 300 ml of water and 200 ml of ethyl acetate, and the organic layer was separated. The mixture was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 3.70 g of Exemplified Compound A-41. Oily.

【0056】

Various forms of the photoconductor are known, and any of them can be used. For example, there is a conductive support provided with a photosensitive layer made of a charge generating substance, a charge transporting substance, and a film-forming binder resin. Further, a laminated photoconductor in which a charge generating layer made of a charge generating substance and a binder resin and a charge transport layer made of a charge transporting substance and a binder resin are provided on a conductive support is also known. .. Either the charge generation layer or the charge transport layer may be the upper layer. Further, if necessary, an undercoat layer is provided between the conductive support and the photosensitive layer, an overcoat layer is provided on the surface of the photosensitive member, and in the case of a laminated photoconductor, an intermediate layer is provided between the charge generating layer and the charge transporting layer. Can also be provided. As a support for producing a photoconductor using the compound of the present invention, a metal drum, a metal plate, conductively processed paper, a sheet-shaped plastic film, a drum-shaped or belt-shaped support, or the like is used. ..

【0057】

Examples of the film-forming binder resin used for forming the photosensitive layer on these supports include various ones depending on the field of application. For example, in the use of photoconductors for copying, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, vinyl chloride / crotonic acid copolymer resin, polyester resin, polyphenylene oxide resin, polyarylate resin, alkyd resin, acrylic resin, methacrylic resin , Phenoxy resin and the like. Among these, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polyarylate resin and the like are excellent in potential characteristics as a photoconductor. Further, these resins can be used alone or as a copolymer of one kind or a mixture of two or more kinds. The amount of these binder resins added to the photoconducting compound is preferably 20 to 1000% by weight, more preferably 50 to 500% by weight.

【0058】

In the case of a laminated photoconductor, these resins contained in the charge generating layer are preferably 10 to 500% by weight, more preferably 50 to 150% by weight, based on the charge generating substance. If the ratio of the resin is too high, the charge generation efficiency is lowered, and if the ratio of the resin is too low, there is a problem in film forming property. Further, these resins contained in the charge transport layer are preferably 20 to 1000% by weight, more preferably 50 to 500% by weight, based on the charge transport substance. If the ratio of the resin is too high, the sensitivity is lowered, and if the ratio of the resin is too low, the characteristics may be repeatedly deteriorated and the coating film may be damaged.

【0059】

Some of these resins are vulnerable to mechanical strength such as pulling, bending, and compression. To improve this property, a substance that imparts plasticity can be added. Specific examples thereof include phthalates (for example, DOP, DBP, etc.), phosphoric acid esters (for example, TCP, TOP, etc.), sebacic acid esters, adipates, nitrile rubbers, chlorinated hydrocarbons, and the like. If these substances are added more than necessary, they adversely affect the electrophotographic characteristics, so the ratio thereof is preferably 20% or less with respect to the binder resin.

【0060】

In addition, an antioxidant, an antioxidant, or the like can be added as an additive to the photoconductor, and a leveling agent or the like can be added as necessary to improve the coatability.

【0061】

The enamine compounds represented by the general formulas (1) and (2) can be used in combination with other charge transporting substances. Charge-transporting substances include hole-transporting substances and electron-transporting substances. Examples of the former include oxadiazoles shown in Japanese Patent Publication No. 34-5466, triphenylmethanes shown in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. Pyrazolines shown in the above, hydrazolines shown in JP-A-55-42380, etc., oxadiazoles shown in JP-A-56-123544, etc. can be mentioned. On the other hand, as electron transporting substances, for example, chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-Tetranitroxanthone, 2,4,8-Trinitrothioxanthone, 1,3,7-Trinitrodibenzothiophene, 1,3,7-Trinitrodibenzothiophene-5,5-dioxide and the like. These charge transporting substances can be used alone or in combination of two or more.

【0062】

Further, it is also possible to add a certain electron-withdrawing compound as a sensitizer that forms a charge transfer complex with the enamine compounds represented by the general formulas (1) and (2) and further enhances the sensitizing effect. Examples of this electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, and phenanthrenquinone, and 4-nitro. Aldehydes such as benzaldehyde, ketones such as 9-benzoylanthraquinone, indandione, 3,5-dinitrobenzophenone, 3,3', 5,5'-tetranitrobenzophenone, phthalic anhydride, 4-chloronaphthalic anhydride, etc. Acid anhydrides, terephthalal malononitrile, 9-anthrylmethyridene malononitrile, 4-nitrobenzalmalononitrile, cyano compounds such as 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide, 3 Examples thereof include phthalides such as-(α-cyano-p-nitrobenzal) phthalide and 3- (α-cyano-p-nitrobenzal) -4,5,6,7-tetrachlorophthalide.

【0063】

The phthalocyanines and the enamine compounds represented by the general formulas (1) and (2) are dissolved or dispersed in an appropriate solvent together with various additives depending on the morphology of the photoconductor, and the coating liquid thereof is used as the conductivity described above. A photoconductor can be produced by applying it on a sex support and drying it.

【0064】

The coating solvent includes halogenated hydrocarbons such as chloroform, dichloroethane, dichloromethane, trichloroethane, trichloroethylene, chlorobenzene and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve and ethylene glycol dimethyl ether. Ether solvents such as, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, cyclohexanone and other ketone solvents, ethyl acetate, methyl formate, methyl cellosolve acetate and other ester solvents, N, N-dimethylformamide, acetonitrile, N-methyl Examples thereof include aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide, alcohol solvents and the like. These solvents can be used alone or as a mixed solvent of two or more kinds.

【0065】

[Example]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

【0066】

Example 1 1 part by weight of τ-type metal-free phthalocyanine and 1 part by weight of polyester resin (Toyobo Byron 220) were mixed with 100 parts by weight of dioxane and dispersed together with glass beads by a paint conditioner for 3 hours. The dispersion liquid thus obtained was applied onto an aluminum-deposited polyester with an applicator and dried to form a charge generation layer having a film thickness of about 0.2 μm. Next, the enamine compound (exemplified compound A-02) was mixed with a polyarylate resin (U-polymer manufactured by Unitica) at a weight ratio of 1: 1 to prepare a 10% solution using dichloroethane as a solvent, and the above charge generation layer was prepared. A charge transport layer having a thickness of about 20 μm was formed by applying it on the surface with an applicator.

【0067】

The laminated photoconductor produced in this way was evaluated for electrophotographic characteristics using an electrostatic recording test device (SP-428 manufactured by Kawaguchi Electric Co., Ltd.). Measurement conditions: Applied voltage -6kV, static No. 3 (turntable rotation speed mode: 10m / min). As a result, the charging potential (Vo) was -800V and the half exposure (E1 / 2) was 1.3 looks / sec, showing high sensitivity values.

【0068】

Furthermore, using this device, the characteristics were evaluated for repeated use with one cycle of charge-static elimination (static elimination light: irradiation with white light for 400 looks x 1 second). When the change in charging potential due to repetition at 5000 times was calculated, the charging potential (Vo) at the 5000th time was -790V, while the charging potential (Vo) at the 1st time was -800V. The characteristics were shown. In addition, the first half-exposure (E1 / 2) was 1.3 lux / sec, while the 5000th half-exposure (E1 / 2) was 1.3 lux / sec, showing excellent characteristics.

【0069】

Examples 2-37 Photoreceptors were prepared in the same manner as in Example 1 except that the phthalocyanines and enamine compounds shown in Tables 2 and 3, respectively, were used instead of the τ-type metal-free phthalocyanine of Example 1 and the exemplified compound A-02. Its characteristics were evaluated. The results are shown in Tables 2 and 3. Table 1 shows the crystal forms of each phthalocyanine used in Examples 1 to 74.

【0070】

[table 1]

<img file="JPH1069107A_D0014.tif" />【0071】

[Table 2]

<img file="JPH1069107A_D0015.tif" />【0072】

[Table 3]

<img file="JPH1069107A_D0016.tif" />【0073】

Example 38 1 part by weight of τ-type metal-free phthalocyanine and 40 parts by weight of tetrahydrofuran were dispersed with glass beads by a paint conditioner device for 4 hours. To the dispersion obtained in this way, 2.5 parts by weight of an enamine compound (exemplified compound A-02), 10 parts by weight of a polycarbonate resin (PCZ-200; manufactured by Mitsubishi Gas Chemical Company), and 60 parts by weight of tetrahydrofuran were added, and a paint conditioner for another 30 minutes was added. After the dispersion treatment with the apparatus, it was applied on the aluminum-deposited polyester with an applicator to form a photoconductor having a thickness of about 15 μm. The electrophotographic characteristics of this photoconductor were evaluated in the same manner as in Example 1. However, only the applied voltage was changed to + 5kV. As a result, the first charging potential (V0) 395V, half exposure (E1 / 2) 1.5 lux / sec, charging potential (V0) 385V after 5000 repetitions, half exposure (E1 / 2) 1.5 lux / sec. It showed excellent characteristics with high sensitivity and little change.

【0074】

Examples 39-74 Photoreceptors were prepared in the same manner as in Example 38, except that the phthalocyanines and enamine compounds shown in Tables 4 and 5, respectively, were used instead of the τ-type metal-free phthalocyanine of Example 38 and the exemplified compound A-02. Its characteristics were evaluated. The results are shown in Tables 4 and 5.

【0075】

[Table 4]

<img file="JPH1069107A_D0017.tif" />【0076】

[Table 5]

<img file="JPH1069107A_D0018.tif" />【0077】

[Chemical 15]

<img file="JPH1069107A_D0019.tif" />【0078】

Comparative example 1 A photoconductor was prepared in the same manner as in Example 1 and its characteristics were evaluated, except that the comparative compound (6) shown above was used instead of the exemplary compound A-02 as the charge transporting substance. As a result, the first charge potential (V0) is -750V and the half exposure (E1 / 2) is 3.1 looks / sec, which is low sensitivity, and the 5000th charge potential (V0) is -525V, half exposure (half exposure). E1 / 2) was 3.2 looks / sec, and a significant decrease in potential was observed due to repetition.

【0079】

[Chemical 16]

<img file="JPH1069107A_D0020.tif" />【0080】

Comparative example 2 A photoconductor was prepared in the same manner as in Example 1 and its characteristics were evaluated, except that the comparative compound (7) shown above was used instead of the exemplary compound A-02 as the charge transporting substance. As a result, the first charge potential (V0) was -720V and the half exposure (E1 / 2) was 1.8 looks / sec, which were relatively good results, but the 5000th charge potential (V0) was -220V. The half-exposure amount (E1 / 2) was 1.5 looks / sec, and a significant decrease in potential was observed due to repetition.

【0081】

[Chemical 17]

<img file="JPH1069107A_D0021.tif" />【0082】

Comparative example 3 A photoconductor was prepared in the same manner as in Example 1 and its characteristics were evaluated, except that the comparative compound (8) shown above was used instead of the τ-type metal-free phthalocyanine as the charge generating substance. As a result, the charging potential (V0) was -755V and the half exposure (E1 / 2) was 3.6 looks / sec, which was insufficient sensitivity.

【0083】

[Chemical 18]

<img file="JPH1069107A_D0022.tif" />【0084】

Comparative example 4 A photoconductor was prepared and its characteristics were evaluated in the same manner as in Example 1, except that the comparative compound (9) was used instead of the τ-type metal-free phthalocyanine as the charge generating substance. As a result, the first charging potential (V0) was -800V and the half exposure (E1 / 2) was 1.7 looks / sec, which were relatively good results, but the 5000th charging potential (V0) was -320V. The half-exposure amount (E1 / 2) was 1.6 looks / sec, and a significant decrease in potential was observed due to repetition.

【0085】

Comparative example 5 A photoconductor was prepared and its characteristics were evaluated in the same manner as in Example 38, except that the comparative compound (6) was used instead of the exemplary compound A-02 as the charge transport material. As a result, the sensitivity of the first charge potential (V0) is 280 V and the half exposure (E1 / 2) is 3.8 looks / sec, and the sensitivity is low, and the 5000th charge potential (V0) is 225 V and half exposure (E1 /). 2) It was 4.1 looks and seconds, and a significant decrease in potential was observed due to repetition.

【0086】

Comparative example 6 A photoconductor was prepared and its characteristics were evaluated in the same manner as in Example 38, except that the comparative compound (7) was used instead of the exemplary compound A-02 as the charge transport material. As a result, the first charge potential (V0) was 360 V and the half exposure (E1 / 2) was 1.9 looks / sec, which was a relatively good result, but the 5000th charge potential (V0) was 120 V, which was halved. The exposure amount (E1 / 2) was 2.5 looks / sec, and a significant decrease in potential and a decrease in sensitivity were observed due to repetition.

【0087】

Comparative example 7 A photoconductor was prepared in the same manner as in Example 38 except that the comparative compound (8) was used instead of the τ-type metal-free phthalocyanine as the charge generating substance, and its characteristics were evaluated. As a result, the charging potential (V0) was 340V and the half exposure (E1 / 2) was 4.8 looks / sec, which was insufficient sensitivity.

【0088】

Comparative Example 8 A photoconductor was prepared in the same manner as in Example 38 except that the comparative compound (9) was used instead of the τ-type metal-free phthalocyanine as the charge generating substance, and its characteristics were evaluated. As a result, the charging potential (V0) was 330V and the half exposure (E1 / 2) was 4.9 looks / sec, which was insufficient sensitivity.

【0089】

From these results, it is possible to obtain a highly sensitive and highly durable electrophotographic photosensitive member by using phthalocyanines as the charge generating substance and the enamine compounds represented by the general formulas (1) and (2) as the charge transporting substance. found.

【0090】

[Effect of the invention]

As is clear from the above, by using the combination of the phthalocyanines and the enamine compound in the present invention, it is possible to provide an electrophotographic photosensitive member having high sensitivity and high durability.

[Simple explanation of drawings]

[Figure 1]

X-ray diffraction spectrum diagram of titanyloxyphthalocyanine (β type) obtained in Synthesis Example 1.

[Figure 2]

IR spectrum diagram of titanyloxyphthalocyanine (β type) obtained in Synthesis Example 1.

[Fig. 3]

X-ray diffraction spectrum diagram of titanyloxyphthalocyanine (amorphous type) obtained in Synthesis Example 1.

[Fig. 4]

X-ray diffraction spectrum diagram of titanyloxyphthalocyanine (Y type) obtained in Synthesis Example 1.

[Fig. 5]

X-ray diffraction spectrum diagram of titanyloxyphthalocyanine (m type).

[Fig. 6]

X-ray diffraction spectrum diagram of diphenoxy germanium phthalocyanine.