JP2003098701A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron transfer substance which can be dispersed in high concentration in a photosensitive layer and has high electron mobility. SOLUTION: The sensitivity of a photosensitive layer is increased by incorporating an electron transfer material comprising a compound expressed by general formula (1) and a charge generating material into the layer. When one kind in oxytitanium phthalocyanine having a specified crystal structure, non- crystalline oxytitanium phthalocyanine, dichlorotin phthalocyanine and nonmetal phthalocyanine is used as the charge generating material, a photosensitive layer having particularly high sensitivity can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the technical field of electrophotographic photoreceptors, and more particularly to an electrophotographic photoreceptor containing an electron transfer material and a phthalocyanine compound.

[0002]

2. Description of the Related Art A single-layer dispersion type photoconductor contains a charge generating material and a charge transfer material in one photosensitive layer, and is a laminated type photoconductor in which the photosensitive layer is functionally separated into a charge generating layer and a charge transfer layer. Compared to this, since the layer structure is small, the manufacturing is easy and the cost is low. However, it has not been put to practical use because there is no electron transfer material having a high electron mobility. Although diphenoquinone shows excellent electron mobility, the electron mobility was insufficient for use in a photoreceptor. Therefore, the present inventors have found that a compound in which an active methylene compound is condensed with quinone has a very excellent electron transfer ability, and realized a single layer dispersion type photoreceptor by using these compounds. However, since high-speed printing is required especially for the photoconductor for printers, research for obtaining a photoconductor with higher sensitivity has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the conventional techniques as described above, and an object thereof is to provide a photosensitive member having high sensitivity.

[0004]

In the process of improving the characteristics of a monolayer dispersion type photoreceptor, the inventors of the present invention charged a specific phthalocyanine compound with an electron transfer material in which a quinone is condensed with an active methylene compound in a photosensitive layer. It has been found that the composition of the present invention exhibits high sensitivity when added as a generating material, and the present invention has been completed. The invention according to claim 1 made on the basis of the above-mentioned findings, comprises a compound represented by the following general formula (1):
7. X-ray diffraction angle (2θ ± 0.2 °) with respect to −Kα ray.
A single-layer dispersion type photoconductor having a photosensitive layer formed by dispersing oxytitanium phthalocyanine having characteristic peaks at 6 ° and 28.6 ° in a resin.

[0005]

[Chemical 21]

(In the general formula (1), the substituent R ₁
To R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) ₂ . Substituent W
Is a ring having a 4-membered ring or more and an 8-membered ring or less, and when the above general formula (1) is rewritten into the following general formula (1 ′),

[0007]

[Chemical formula 22]

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. The invention according to claim 2 is the single-layer dispersion type photoreceptor according to claim 1, wherein the compound represented by the general formula (1) is represented by the general formula (2).
Is a single-layer dispersion type photoreceptor.

[0009]

[Chemical formula 23]

(In the general formula (2), the substituent R ₁
To R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 3 is the single-layer dispersion type photoreceptor according to claim 1, wherein the compound represented by the general formula (1) is represented by the general formula (3):
Is a single-layer dispersion type photoreceptor.

[0011]

[Chemical formula 24]

(In the above general formula (3), the substituent R ₁
To R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 4 is a compound represented by the following general formula (1) and an X-ray diffraction angle (2θ ± 0.
A single-layer dispersion type photoconductor having a photosensitive layer in which oxytitanium phthalocyanine having a characteristic peak at 27.2 ° at 2 °) is dispersed in a resin.

[0013]

[Chemical 25]

(In the general formula (1), the substituent R ₁
To R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) ₂ . Substituent W
Is a ring having a 4-membered ring or more and an 8-membered ring or less, and when the above general formula (1) is rewritten into the following general formula (1 ′),

[0015]

[Chemical formula 26]

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. The invention according to claim 5 is the single-layer dispersion type photoreceptor according to claim 4, wherein the compound of the general formula (1) is represented by the general formula (2).
Is a single-layer dispersion type photoreceptor.

[0017]

[Chemical 27]

(In the general formula (2), the substituent R ₁
To R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. According to a sixth aspect of the present invention, in the single-layer dispersion type photoconductor according to the fourth aspect, the compound represented by the general formula (1) is represented by the general formula (3).
Is a single-layer dispersion type photoreceptor.

[0019]

[Chemical 28]

(In the above general formula (3), the substituent R ₁
To R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 7 is the compound represented by the following general formula (1) and an X-ray diffraction angle (2θ ± 0.2 with respect to Cu—Kα ray.
A single-layer dispersion type photoreceptor having a photosensitive layer formed by dispersing oxytitanium phthalocyanine which does not show a characteristic peak at (°) in a resin.

[0021]

[Chemical 29]

(In the general formula (1), the substituent R ₁
To R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) ₂ . Substituent W
Is a ring having a 4-membered ring or more and an 8-membered ring or less, and when the above general formula (1) is rewritten into the following general formula (1 ′),

[0023]

[Chemical 30]

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. The invention according to claim 8 is the single-layer dispersion type photoreceptor according to claim 7, wherein the compound of the general formula (1) is represented by the general formula (2).
Is a single-layer dispersion type photoreceptor.

[0025]

[Chemical 31]

(In the general formula (2), the substituent R ₁
To R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 9 is the single-layer dispersion type photoreceptor according to claim 7, wherein the compound of the general formula (1) is represented by the general formula (3).
Is a single-layer dispersion type photoreceptor.

[0027]

[Chemical 32]

(In the general formula (3), the substituent R ₁
To R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 10 is a single-layer dispersion type photoreceptor having a photosensitive layer in which a compound represented by the following general formula (1) and dichlorotin phthalocyanine are dispersed in a resin. .

[0029]

[Chemical 33]

(In the general formula (1), the substituent R ₁
To R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) ₂ . Substituent W
Is a ring having a 4-membered ring or more and an 8-membered ring or less, and when the above general formula (1) is rewritten into the following general formula (1 ′),

[0031]

[Chemical 34]

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. The invention according to claim 11 is the single layer dispersion type photoreceptor according to claim 10, wherein the compound of the general formula (1) is represented by the general formula (2). Type photoconductor.

[0033]

[Chemical 35]

(In the general formula (2), the substituent R ₁
To R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 12 is the single-layer dispersion type photoreceptor according to claim 10, wherein the compound represented by the general formula (1) is represented by the general formula (3). Type photoconductor.

[0035]

[Chemical 36]

(In the above general formula (3), the substituent R ₁
To R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. According to a thirteenth aspect of the present invention, in the single-layer dispersion type photoconductor according to the tenth aspect, the dicycloroszuphthalocyanine has an X-ray diffraction angle (2θ ± 0.2) with respect to Cu—Kα rays.
°) has a maximum peak at 10.5 ° and has a peak intensity in the range of 5 ° to 9 ° of 10% or less of the peak intensity of 10.5 °. Is.

According to a fourteenth aspect of the present invention, there is provided a single-layer dispersion type photoreceptor having a photosensitive layer in which a compound represented by the following general formula (1) and a metal-free phthalocyanine are dispersed in a resin. Is.

[0038]

[Chemical 37]

(In the general formula (1), the substituent R ₁
To R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) ₂ . Substituent W
Is a ring having a 4-membered ring or more and an 8-membered ring or less, and when the above general formula (1) is rewritten into the following general formula (1 ′),

[0040]

[Chemical 38]

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. The invention according to claim 15 is the single-layer dispersion type photoreceptor according to claim 14, wherein the compound of the general formula (1) is represented by the general formula (2). Type photoconductor.

[0042]

[Chemical Formula 39]

(In the general formula (2), the substituent R ₁
To R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. The invention according to claim 16 is the single-layer dispersion type photoreceptor according to claim 14, wherein the compound of the general formula (1) is represented by the general formula (3). Type photoconductor.

[0044]

[Chemical 40]

(In the general formula (3), the substituent R ₁
To R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. )

BEST MODE FOR CARRYING OUT THE INVENTION The single-layer dispersion type photoconductor of the present invention can improve the photoconductor sensitivity by combining the compound represented by the general formula (1) with a specific phthalocyanine. . The single-layer dispersion type photoconductor of the present invention has the layer structure shown in FIG. 7 as an example. Reference numeral 10 in FIG. 7 indicates a single-layer dispersion type photoconductor. The single-layer dispersion type photoreceptor 10 has a conductive support 11 and a photosensitive layer 12, and the photosensitive layer 1
The charge generating material 2 has a charge generating material and an electron transfer material dispersed in a resin.

As another example of the present invention, the conductive support 11
An undercoat layer may be provided between the photosensitive layer 12 and the photosensitive layer 12, and
A protective layer may be provided on the photosensitive layer 12. Furthermore,
The undercoat layer and the protective layer may be provided at the same time.
Various methods can be used to form the photosensitive layer 12, but in the usual case, a charge generating material and an electron transfer material are dispersed or dissolved together with a resin in a suitable solvent to prepare a coating solution, The coating solution is applied on the base,
A method of drying can be used. The film thickness of the photosensitive layer 12 is not particularly limited, but is preferably about 5 μm or more and 50 μm or less, and particularly preferably about 10 μm or more and 35 μm or less. If the thickness of the photosensitive layer 12 is thin, the sensitivity of the photosensitive member is improved, but the durability against film loss is deteriorated, and if it is increased, the durability is improved but the sensitivity tends to be decreased. The electron transfer material used in the present invention is represented by the general formula (1), and this electron transfer material has a high electron mobility and is suitable for a single layer dispersion type photoreceptor.

[0047]

[Chemical 41]

(In the general formula (1), the substituent R ₁
To R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) ₂ . Substituent W
Is a ring having a 4-membered ring or more and an 8-membered ring or less, and when the above general formula (1) is rewritten into the following general formula (1 ′),

[0049]

[Chemical 42]

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. ) Specific examples of general formula (1) are shown in the following Tables A (1) to A (26), but the present invention is not limited thereto.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Table 7]

[0058]

[Table 8]

[0059]

[Table 9]

[0060]

[Table 10]

[0061]

[Table 11]

[0062]

[Table 12]

[0063]

[Table 13]

[0064]

[Table 14]

[0065]

[Table 15]

[0066]

[Table 16]

[0067]

[Table 17]

[0068]

[Table 18]

[0069]

[Table 19]

[0070]

[Table 20]

[0071]

[Table 21]

[0072]

[Table 22]

[0073]

[Table 23]

[0074]

[Table 24]

[0075]

[Table 25]

[0076]

[Table 26]

In the above general formula (1), the electron transfer materials represented by the following general formulas (2) and (3) are preferable because of their higher mobility.

[0078]

[Chemical 43]

(In the general formula (2), the substituent R ₁
To R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. )

[0080]

[Chemical 44]

(In the general formula (3), the substituent R ₁
To R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An allyl group, an amide group, an amino group,
It is any one kind of substituent selected from the group consisting of an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur, and ═C (CN) _2, and substituent Y is composed of either oxygen or sulfur. )

Further, in the general formulas (2) and (3), the substituents X and Y are oxygen, and R ₁ and R ₃ are t-.
A compound in which the Bu group and R ₂ and R ₄ are hydrogen is more preferable because of easy production and high mobility. Specific examples of the compound represented by the general formula (1) are shown in Tables B (1) to B (4) below, but the invention is not limited thereto.

[0083]

[Table 27]

[0084]

[Table 28]

[0085]

[Table 29]

[0086]

[Table 30]

The photosensitive layer 12 may contain one type of the compound represented by the general formula (1), or two or more types thereof. The concentration of the compound represented by the general formula (1) in the photosensitive layer 12 is not particularly limited as it varies depending on the required photoreceptor performance and charging polarity, but is preferably 0.1% by weight or more and 70% by weight or less. If the concentration is low, the electron transfer may be insufficient and the characteristics of the photoconductor may be affected.If the concentration is high, the compatibility with the resin may be poor and a non-uniform film may be formed or the resin concentration may be low, resulting in poor film strength. It may decrease. As the charge generating material used in the present invention, oxytitanium phthalocyanine having characteristic peaks at 7.6 ° and 28.6 ° in X-ray diffraction angle (2θ ± 0.2 °) with respect to Cu-Kα ray,
Oxytitanium phthalocyanine having a characteristic peak at 27.3 °, oxytitanium phthalocyanine not showing a characteristic peak, dichlorotin phthalocyanine and metal-free phthalocyanine can be used.

X-ray diffraction angle (2θ ±
Oxytitanium phthalocyanine having characteristic peaks at 7.6 ° and 28.6 ° at 0.2 ° shows an X-ray diffraction pattern as shown in FIG. 1, for example. Although the maximum peak is 7.6 ° in FIG. 1, the maximum peak may be 28.6 °. In addition to these peaks, 12.5 °, 13.
Clear peaks are shown at 3 °, 22.5 °, and 25.4 °, but those peaks are broad (split), split (split), and shift (change in angle) depending on the crystal state and measurement conditions. ) Is possible.

X-ray diffraction angle (2θ ±
Oxytitanium phthalocyanine having a characteristic peak at 27.2 ° at 0.2 ° shows an X-ray diffraction pattern as shown in FIG. 2, for example. Other than 27.2 °, 9.5, 1
It also shows peaks at 4.2 and 24.1 °, but these peaks may be broadened, splitted, or shifted depending on the crystal state and measurement conditions. Oxytitanium phthalocyanine which does not show a characteristic peak is amorphous oxytitanium phthalocyanine,
For example, an X-ray diffraction diagram as shown in FIG. 3 is shown. As shown in FIG. 3, a clear peak is not shown, but a broad peak may be seen.

Dichlorotin phthalocyanine has SnCl ₂ as the central metal of phthalocyanine. As the crystal form of dichlorotin phthalocyanine, the maximum peak at 10.5 ° in the X-ray diffraction angle (2θ ± 0.2 °) described in JP-A No. 11-286618 has a maximum peak of 5 ° to 9 °. The peak intensity in the range of 10% or less of the peak intensity at 10.5 °, JP-A-5-14047.
X-ray diffraction angle (2θ ± 0.2 °) described in Japanese Patent Publication No. 2
At 8.7 °, 9.9 °, 10.9 °, 13.1 °, 1
5.2 °, 16.3 °, 17.4 °, 21.9 °, 2
5.5 ° or 9.2 °, 12.2 °, 13.4
Those exhibiting strong diffraction peaks at °, 14.6 °, 17.0 °, 25.3 °, or at the X-ray diffraction angle (2θ ± 0.2 °) described in JP-A-6-228453. 8.4
°, 10.6 °, 12.2 °, 13.8 °, 16.0
°, 16.5 °, 17.4 °, 19.1 °, 22.4
°, 28.2 °, 30.0 °, or 8.4 °, 1
1.2 °, 14.6 °, 15.6 °, 16.9 °, 1
8.6 °, 19.6 °, 25.7 °, 27.2 °, 2
Those having a strong diffraction peak at 8.5 ° can be used. Among them, the X-ray diffraction angle (2θ ± 0.2 °) is 10.5 °
It is particularly preferable that the peak intensity is in the range of 5 ° to 9 ° and the peak intensity is 10% or less of the peak intensity of 10.5 °. The X-ray diffraction pattern of this crystal form is shown in FIG.

The metal-free phthalocyanine is a phthalocyanine having no central metal. Many crystal forms have been reported as metal-free phthalocyanines, but any form may be used. Especially, the X-ray diffraction angle (2θ ± 0.2 °) is 7.5 °,
9.1 °, 15.1 °, 16.6 °, 17.3 °, 18.
5 °, 22.2 °, 23.8 °, 25.9 °, 27.2
Those having strong diffraction peaks at 9 ° and 28.6 ° are preferable. The X-ray diffraction pattern of this crystal form is shown in FIG. Photosensitive layer 12
The concentration of the charge generating material therein is generally 0.005% by weight or more and 70% by weight or less, and preferably 1% by weight or more and 10% by weight or less. When the concentration of the charge generating material is low, the sensitivity of the photoreceptor tends to decrease, and when the concentration is high, the potential holding ratio and the film strength tend to decrease.

As the conductive support 11 in the photoreceptor 10 of the present invention, aluminum, brass, stainless steel, nickel, chromium, titanium, gold, silver, copper, tin, platinum, molybdenum, indium or the like, or a single metal thereof. Alloyed bodies can be used. A thin film of a conductive substance may be further formed on the surface of the above metal or alloy by vapor deposition, plating or the like. Although the conductive support 11 itself may be made of a conductive material, a thin film of the above metal or carbon is formed on the surface of the non-conductive plastic plate or film by a method such as vapor deposition or plating to improve the conductivity. You may have it.

When a resin is used as the conductive support 11, a conductive agent such as metal powder or conductive carbon may be contained in the resin, or a conductive resin may be used as the base forming resin. Further, when glass is used for the conductive support 11, the surface thereof may be coated with tin oxide, indium oxide, or aluminum iodide so as to have conductivity.
The type and shape are not particularly limited, and the conductive support 11 can be formed using various materials having conductivity.

Generally, as the conductive support 11, a cylindrical aluminum tube alone, its surface anodized, or an aluminum tube with an undercoat layer formed thereon is often used. This undercoat layer has a function of improving adhesion, a barrier function of preventing an inflow current from the aluminum tube,
It has the function of covering defects on the surface of aluminum tubes. This undercoat layer includes polyethylene resin, acrylic resin, epoxy resin, polycarbonate resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, polyamide resin, nylon resin, alkyd resin, melamine resin, polyimide resin, etc. Various resins can be used. These undercoat layers may be made of a single resin or a mixture of two or more kinds of resins. Further, a metal compound, carbon, silica, resin powder or the like can be dispersed in the layer. Further, various pigments, electron-accepting substances, electron-donating substances, etc. may be incorporated for improving the characteristics.

In the photosensitive layer 12, other phthalocyanine pigments or azo pigments may be mixed with the phthalocyanine composition of the present invention in order to obtain appropriate photosensitivity wavelength and sensitizing action. These are desirable because they are compatible with each other in sensitivity. In addition, for example, monoazo pigments, bisazo pigments, trisazo pigments, polyazo pigments, indigo pigments, slene pigments, toluidine pigments, pyrazolone pigments, perylene pigments, quinacridone pigments, pyrylium salts and the like can be used.

As the resin for forming the photosensitive layer 12, polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, chlorinated polyether, vinyl chloride- Vinyl acetate resin, polyester resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin, epoxy resin, polyarylate resin, diarylate resin, polysulfone resin, polyethersulfone resin, polyallyl resin Sulfone resin, silicone resin, ketone resin, polyvinyl butyral resin,
There are resins such as polyether resin, phenol resin, EVA (ethylene / vinyl acetate) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene) resin, ABS (acrylonitrile / butadiene / styrene) resin and epoxy arylate. They may be used alone or in a mixture of two or more. It is preferable to use a mixture of resins having different molecular weights because the hardness and abrasion resistance can be improved.

The solvent used for the coating solution is methanol,
Alcohols such as ethanol, n-propanol, i-propanol and butanol, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, aromatic hydrocarbons such as toluene and xylene, dichloromethane, dichloroethane, Chlorinated hydrocarbons such as chloroform and chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran (TH
F), ethers such as methoxyethanol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl formate, propyl formate,
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate,
Examples include esters such as methyl propionate, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, dioxane, ether solvents such as anisole, N, N-dimethylformamide, dimethyl sulfoxide, and the like.

Of these, a ketone solvent, an ester solvent, an ether solvent, or a halogenated hydrocarbon solvent is particularly preferable, and these can be used alone or as a mixed solvent of two or more kinds. Further, other charge transfer material can be added to the photoreceptor of the present invention. In that case, since the sensitivity can be increased and the residual potential can be decreased, the characteristics of the electrophotographic photosensitive member of the present invention can be improved. In particular, it is preferable to add a hole transfer material in terms of characteristics. When the hole transfer material is added, the concentration of the hole transfer material in the photosensitive layer 12 is not particularly limited because it varies depending on the required photoreceptor performance and charging polarity.
It is preferably 0.1% by weight or more and 70% by weight or less.

Charge transfer materials that can be added to improve such properties include polyvinyl carbazole, halogenated polyvinyl carbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine, polyvinyl pyrazoline, polyacetylene. High conductivity of polythiophene, polypyrrole, polyphenylene, polyphenylene vinylene, polyisothianaphthene, polyaniline, polydiacetylene, polyheptadiene, polypyridinediyl, polyquinoline, polyphenylene sulfide, polyferrocenylene, polyperinaphthylene, polyphthalocyanine, etc. Molecular compounds can be used.
Further, as low molecular weight compounds, trinitrofluorenone, tetracyanoethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof, polycyclic aromatic compounds such as anthracene, pyrene, phenanthrene, indole, carbazole. , Nitrogen-containing heterocyclic compounds such as imidazole, fluorenone, fluorene, oxadiazole, oxazole,
Pyrazoline, hydrazone, triphenylmethane, triphenylamine, enamine, stilbene, butadiene compound and the like can be used.

A polymer solid electrolyte obtained by doping a polymer compound such as polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethacrylic acid with a metal ion such as lithium (Li) ion can also be used. Furthermore, an organic charge transfer complex formed of an electron-donating compound and an electron-accepting compound represented by tetrathiafulvalene-tetracyanoquinodimethane can also be used, and even if only one of these is added, Even if two or more compounds are mixed and added, desired photoconductor characteristics can be obtained.

The coating liquid for producing the photoconductor of the present invention may contain the electrophotographic photoconductor in a range not impairing the characteristics thereof.
Antioxidant, ultraviolet absorber, radical scavenger, softener,
By adding a curing agent, crosslinking agent, etc., the characteristics, durability, and
It is possible to improve mechanical properties. Furthermore, by adding a dispersion stabilizer, an anti-settling agent, an anti-color separation agent, a leveling agent, a defoaming agent, a thickener, a matting agent, etc., the finished appearance of the photoreceptor and the life of the coating liquid can be improved. .

In addition, an organic thin film such as an epoxy resin, a melamine resin, a polyvinyl formal resin, a polycarbonate resin, a fluororesin, a polyurethane resin or a silicone resin, or a hydrolyzate of a silane coupling agent is formed on the photosensitive layer 12. A protective layer may be provided by forming a thin film of the siloxane structure. In that case, the durability of the photoreceptor is improved, which is preferable. This protective layer may be provided to improve other functions other than the improvement of durability.

[0103]

EXAMPLES Examples of electrophotographic photosensitive members according to the present invention will be described in detail below. <Specific Examples of Single-Layer Dispersion Type Negatively Charged Photosensitive Member><Examples 1 to 21> 1 part by weight of oxytitanium phthalocyanine showing an X-ray diffraction diagram shown in FIG. 1 as a charge generating material, and 10 parts by weight of polycarbonate as a binder resin. And 80 parts by weight of THF are kneaded and dispersed as a solvent, and 9 parts by weight of the compound represented by the formulas (4) to (24) as an electron transfer material and the trivalent compound represented by the following formula (25) as a hole transfer material A coating solution was prepared by dissolving 2 parts by weight of the phenylamine compound.

[0104]

[Chemical formula 45]

Then, this coating solution was used to dip-coat on the aluminum drum which is the conductive support 11,
By drying at 1 ° C. for 1 hour, a photosensitive layer having a film thickness of 20 μm and having both charge generation and charge transfer was formed to prepare a single layer dispersion type negative charging photoreceptor. Tables C (1) show the combinations of the charge generation material and the electron transfer material as Examples 1 to 21, respectively. In addition, among Examples 1 to 21, Example 1 is a case where the compound represented by the general formula (2) is used as an electron transfer material, and Examples 2 to 4 and 7 to 21 are electron transfer materials. This is the case where the compound represented by the general formula (3) is used.

[0106]

[Table 31]

The photosensitive layer of the electrophotographic photosensitive member produced as described above was dissolved in 4-methoxy-4-methylpentanone, and a membrane filter (pore size: 0.2 μm) was dissolved.
After the charge-generating material was filtered with, dried, and then subjected to X-ray diffraction analysis under the following conditions, a pattern showing a diffraction peak at the same position as in FIG. 1 was obtained. This charge generation material shows characteristic peaks at 7.6 ° and 28.6 °.

X-ray diffraction analysis conditions X-ray source: Cu-Kα tube voltage, current: 45 kv, 40 mA Measurement range: 5 to 30 ° (Note that the X-ray diffraction charts shown in FIGS. 2 to 6 are also under the above analysis conditions. The measurement was carried out.The horizontal axis of the X-ray diffraction charts in FIGS.
And the vertical axis represents the detection intensity of X-rays. <Examples 22 to 42> A monolayer was formed in the same manner as in Examples 1 to 21 except that the charge generating material was replaced with oxytitanium phthalocyanine showing the X-ray diffraction diagram shown in FIG. A dispersion type negatively charged photoreceptor was produced. The combinations of the charge generating material and the electron transfer material are shown in Table C (2) as Examples 22 to 42, respectively. In addition, of the examples 22 to 42, the example 22 is an electron transfer material having the above general formula (2)
In the case of using the compound represented by
5, 28 to 42 are electron transfer materials represented by the general formula (3).
This is the case when the compound represented by

[0109]

[Table 32]

<Examples 43 to 63> Examples 43 to 63 are the same as Examples 1 to 21 except that the charge generating material is replaced with oxytitanium phthalocyanine showing the X-ray diffraction diagram shown in FIG. A single layer dispersion type negative charging photoreceptor was produced. The combinations of the charge generation material and the electron transfer material are shown in Table C (3) as Examples 43 to 63, respectively. Example 4
Of Examples 3 to 63, Example 43 is a case where the compound represented by the general formula (2) is used as the electron transfer material, and Examples 44 to 46 and 49 to 63 are the general formula ( This is the case when the compound represented by 3) is used.

[0111]

[Table 33]

<Examples 64 to 84> Examples 1 to 21 are the same as Examples 1 to 21, except that the charge generating material is replaced by dichlorotin phthalocyanine showing the X-ray diffraction diagram shown in FIG.
A single-layer dispersion type negative charging photoreceptor was prepared in the same manner as 21.
The combinations of the charge generating material and the electron transfer material are shown in Table C (4) as Examples 64 to 84, respectively. Incidentally, from Example 64 to
Of the 84, Example 64 is a case where the compound represented by the general formula (2) is used as the electron transfer material, and Examples 65 to 67 and 70 to 84 are the general formula (3) as the electron transfer material. This is the case when the compound represented by

[0113]

[Table 34]

<Examples 85 to 105> Examples 1 to 21 except that the charge generating material is replaced with a metal-free phthalocyanine showing an X-ray diffraction diagram shown in FIG.
A single-layer dispersion type negative charging photoreceptor was prepared in the same manner as in. The combinations of the charge generation material and the electron transfer material are shown in Table C (5) as Examples 85 to 105, respectively. Incidentally, Examples 85-1
Of Examples 05, Example 85 is a case where the compound represented by the general formula (2) is used as the electron transfer material, and Examples 86 to 88 and 91 to 105 are the general formula (3) as the electron transfer material. This is the case when the compound represented by

[0115]

[Table 35]

Comparative Examples 1 to 21 Example 1 except that the charge generating material was replaced with oxytitanium phthalocyanine showing the X-ray diffraction diagram shown in FIG. 6 in Examples 1 to 21.
In the same manner as in No. 21 to No. 21, single-layer dispersion type negative charging photoreceptors were produced. Tables C (6) show the combinations of the charge generation material and the electron transfer material, respectively, as Comparative Examples 1 to 21. The oxytitanium phthalocyanine shown in FIG. 6 shows a characteristic peak at 26.3 °.

[0117]

[Table 36]

<Comparative Examples 22 to 27> In Examples 1 to 21, the electron transfer material was replaced with the compound represented by the following formula (26), and the charge generating material was changed as shown in Table C (7). A single layer dispersion type negative charging photoreceptor was produced. Comparative Example 22
~ 27.

[0119]

[Chemical formula 46]

[0120]

[Table 37]

<Specific Examples of Single Layer Dispersion Type Positively Charged Photosensitive Member><Examples 106 to 126> 1 part by weight of oxytitanium phthalocyanine showing an X-ray diffraction diagram shown in FIG. 1 as a charge generating material, and a binder resin. 10 parts by weight of polycarbonate is kneaded and dispersed using 80 parts by weight of THF as a solvent, and 2 parts by weight of a compound represented by the formulas (4) to (24) as an electron transfer material and a compound represented by formula (25) as a hole transfer material. A coating solution was prepared by dissolving 8 parts by weight of the triphenylamine compound. Then, using this coating solution, it is applied by dip coating on an aluminum drum which is the conductive support 11 and dried at 80 ° C. for 1 hour to form a photosensitive layer having a film thickness of 20 μm and having both charge generation and charge transfer. A single layer dispersion type positively charged photoreceptor was produced. Tables C (8) show the combinations of the charge generation material and the electron transfer material for Examples 106 to 126, respectively. In addition, among Examples 106 to 126, Example 106 is a case where the compound represented by the above general formula (2) is used as an electron transfer material, and Examples 107 to 109 and 112 to
126 is a case where the compound represented by the above general formula (3) is used as the electron transfer material.

[0122]

[Table 38]

<Examples 127-147> Example 106-
In 126, a single-layer dispersion type negative charging photoreceptor was produced in the same manner as in Examples 106 to 126 except that the charge generating material was replaced with oxytitanium phthalocyanine showing the X-ray diffraction diagram shown in FIG. Examples 127 to 147, respectively,
Table C (9) shows combinations of charge generation materials and electron transfer materials.
Shown in. Incidentally, of the examples 127 to 147, the example 12
No. 7 is a case where the compound represented by the above general formula (2) was used as the electron transfer material, and Examples 128 to 130 and 13 were used.
3-147 is the case where the compound represented by the above general formula (3) is used as the electron transfer material.

[0124]

[Table 39]

<Examples 148 to 168> Examples 106 to
In 126, a single-layer dispersion type negative charging photoreceptor was produced in the same manner as in Examples 106 to 126 except that the charge generating material was replaced with oxytitanium phthalocyanine showing the X-ray diffraction diagram shown in FIG. Examples 148 to 168 respectively,
Table C (1) shows the combinations of charge generation materials and electron transfer materials.
0). In addition, among Examples 148 to 168, Example 148 is a case where the compound represented by the general formula (2) is used as an electron transfer material, and Examples 149 to 151,
154 to 168 are electron transfer materials represented by the general formula (3).
This is the case when the compound represented by

[0126]

[Table 40]

<Examples 169 to 189> Example 106 to
In 126, a single-layer dispersion type negative charging photoreceptor was produced in the same manner as in Examples 106 to 126 except that the charge generating material was replaced with dichlorotin phthalocyanine showing the X-ray diffraction diagram shown in FIG. Tables C (11) show the combinations of the charge generation material and the electron transfer material, respectively, as Examples 169 to 189. Incidentally, of the examples 169 to 189, the example 169
Is the case where the compound represented by the general formula (2) is used as the electron transfer material, and Examples 170 to 172 and 175 are used.
To 189 are the cases where the compound represented by the general formula (3) is used as the electron transfer material.

[0128]

[Table 41]

<Examples 190-210> Example 106-
In 126, a single-layer dispersion type negative charging photoreceptor was produced in the same manner as in Examples 106 to 126 except that the charge generating material was replaced with a metal-free phthalocyanine showing an X-ray diffraction diagram shown in FIG. The combinations of the charge generation material and the electron transfer material are shown in Table C (12) as Examples 190 to 210, respectively.
Note that, among Examples 190 to 210, Example 190 is a case where the compound represented by the general formula (2) is used as an electron transfer material, and Examples 190 to 193 and 196 to 21.
0 is the case where the compound represented by the general formula (3) is used as the electron transfer material.

[0130]

[Table 42]

<Comparative Examples 28 to 48> Examples 106 to 12
In Example 6, a single layer dispersion type negative charging photoreceptor was produced in the same manner as in Examples 106 to 126 except that the charge generating material was replaced with oxytitanium phthalocyanine showing the X-ray diffraction diagram shown in FIG. Tables C (13) show combinations of the charge generation material and the electron transfer material, which are Comparative Examples 28 to 48, respectively.

[0132]

[Table 43]

<Comparative Examples 49 to 54> Examples 106 to 12
6, the electron transfer material was replaced with the compound represented by the formula (26), and the charge generation material was changed as shown in Table C (14) to prepare a single-layer dispersion type negative charging photoreceptor. These are Comparative Examples 49 to 54, respectively.

[0134]

[Table 44]

<Conditions for Measuring Single Layer Dispersion Type Negatively Charged Photosensitive Member> The corona discharger was set so that the corona discharge current was 17 μA, and the single layer dispersion type prepared in Examples 1 to 105 and Comparative Examples 1 to 27 was prepared. The photoconductor was negatively charged by corona discharge in the dark, and the charge potential was measured. The surface potential at this time is the initial charge potential (V). After that, the surface potential of the photoreceptor is
The discharge current was adjusted to 700 V and exposed with light of 780 nm, and the surface potential of each photoconductor was changed from -700 V to -3.
The amount of exposure to be halved to 50 was measured. The exposure dose at this time is defined as a half exposure dose (μJ / cm ² ). This half exposure amount is a value indicating the sensitivity of the photoconductor.

Further, the surface potential of each photoconductor is -700 V and is 7
The surface potential when irradiated with 80 nm light (exposure energy 10 μJ / cm ² ) was measured. The surface potential at this time is the residual potential (V). After that, the surface potential of the photoconductor was charged again so that the surface potential of the photoconductor became −700 V, and the surface potential V10 when left in a dark place for 10 seconds was measured. Potential retention rate (%) = V
10 / −700 × 100 is calculated. This potential holding rate is an index showing the insulating property of the photoconductor.

The above measurement was carried out in the LL environment (temperature 15 ° C., humidity 1
5%), NN environment (temperature 25 ° C, humidity 40%), HH environment (temperature 35 ° C, humidity 80%). Obtain the average of the half-exposure amount of each photoconductor in three environments,
The value obtained by squaring the difference from the half-exposure amount of each photoconductor under each environment is calculated as a sensitivity environmental stability index. The sensitivity environmental stability index is represented by the following formula (1).

[0138] (average of half decay exposure -3 half decay exposure environment of NN environment) Sensitivity environmental stability index = (average of half decay exposure -3 half decay exposure environment of LL environment) ² + ² + ( HH environment half-exposure-3 average half-exposure under environment) ² (Equation 1) This value indicates the magnitude of fluctuation in the sensitivity of the photoreceptor to the environment.
A smaller value indicates that the sensitivity of the photoconductor does not change even if the environment changes.

<Conditions for Measuring Single-Layer Dispersion Type Positively Charged Photoreceptor> The corona discharger was set so that the corona discharge current was 17 μA, and the single-layer dispersion type produced in Examples 106 to 210 and Comparative Examples 28 to 54. The photoconductor was positively charged by corona discharge in the dark and the charge potential was measured. The surface potential at this time is the initial charge potential (V). After that, the discharge current is adjusted so that the surface potential of the photoconductor becomes 700V, and 780n
m light to expose the surface potential of each photoconductor from 700V to 3
The amount of exposure to be halved to 50 was measured. The exposure dose at this time is defined as a half exposure dose (μJ / cm ² ). This half exposure amount is a value indicating the sensitivity of the photoconductor.

Further, the surface potential of each photoconductor is 78 V at 78V.
The surface potential when irradiated with 0 nm light (exposure energy 10 μJ / cm ² ) was measured. The surface potential at this time is the residual potential (V). After that, the surface potential of the photoconductor becomes 7 again.
The surface potential V10 when charged to 00 V and left in a dark place for 10 seconds was measured, and the potential holding ratio (%) = V10.
Calculate / 700 × 100. This potential holding rate is an index showing the insulating property of the photoconductor.

The above measurement was performed in the LL environment (temperature 15 ° C., humidity 1
5%), NN environment (temperature 25 ° C, humidity 40%), HH environment (temperature 35 ° C, humidity 80%). Obtain the average of the half-exposure amount of each photoconductor in three environments,
The value obtained by squaring the difference from the half-exposure amount of each photoconductor under each environment is calculated as a sensitivity environmental stability index.

<Measurement Results> The measurement results of Examples 1 to 105 and Comparative Examples 1 to 27 are as shown in Table D (1) to Table D (6).

[0143]

[Table 45]

[0144]

[Table 46]

[0145]

[Table 47]

[0146]

[Table 48]

[0147]

[Table 49]

[0148]

[Table 50]

Examples 106 to 210 and Comparative Examples 28 to 5
The measurement results of No. 4 are as shown in Table D (7) to Table D (12).

[0150]

[Table 51]

[0151]

[Table 52]

[0152]

[Table 53]

[0153]

[Table 54]

[0154]

[Table 55]

[0155]

[Table 56]

Comparing the above example with the comparative example, it can be seen that a photosensitive member having a small half-exposure amount and high sensitivity was obtained in the example. Among the charge generating materials contained in the single layer dispersion type photoreceptor of the present invention, 7.6 ° and 28.6 ° by X-ray diffraction analysis.
Examples 1 to 21 and Examples 106 to 126 using oxytitanium phthalocyanine having a characteristic peak at
Indicates that the environmental stability index is smaller than the values of the photoconductors using other charge generating materials, and the characteristics do not change even if the environment changes.

Also, Examples 43 to 63 and Examples 148 to 16 using amorphous oxytitanium phthalocyanine.
It can be seen that No. 8 is superior in chargeability and potential holding ratio to the single layer dispersion type photoreceptor containing another charge generating material.
Furthermore, Example 64 using dichlorotin phthalocyanine
~ 84 and Examples 169 to 189 are characterized by high chargeability and low environmental stability index.

[0158]

As described above, the single layer dispersion type photoreceptor of the present invention has high sensitivity.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction pattern of oxytitanium phthalocyanine having characteristic peaks at 7.6 ° and 28.6 °.

FIG. 2 is an X-ray diffraction pattern of oxytitanium phthalocyanine having a characteristic peak at 27.2 °.

FIG. 3 is an X-ray diffraction pattern of oxytitanium phthalocyanine showing no characteristic peak.

FIG. 4 X-ray diffraction pattern of dichlorotin phthalocyanine

FIG. 5: X-ray diffraction pattern of metal-free phthalocyanine

FIG. 6 is an X-ray diffraction pattern of oxytitanium phthalocyanine having a characteristic peak at 26.3 °.

FIG. 7 is a sectional view showing an example of a single-layer dispersion type photoconductor.

[Explanation of symbols]

10 ... Single layer dispersion type photoreceptor 11 ... Conductive support 12 ... Photosensitive layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuyuki Kiuchi             29 shares, 14 Torihama-cho, Kanazawa-ku, Yokohama-shi, Kanagawa             Ceremony Company Permachem Asia (72) Inventor Toyozo Sato             29 shares, 14 Torihama-cho, Kanazawa-ku, Yokohama-shi, Kanagawa             Ceremony Company Permachem Asia (72) Inventor Hiroki Suzuki             1014 Miyahara-cho, Kofu City, Yamanashi Prefecture Yamanashi Electronics             Business (72) Inventor Hyakusetsu Mitsuyo             No.44-302, Shimogawaracho, Kofu City, Yamanashi Prefecture (72) Inventor Tadayoshi Uchida             1014 Miyahara-cho, Kofu City, Yamanashi Prefecture Yamanashi Electronics             Business F term (reference) 2H068 AA14 AA19 AA31 BA16 BA17                       BA38 BA39 BA63 FA13

Claims (16)

[Claims] 1. A compound represented by the following general formula (1), and C:
Oxytitanium phthalocyanine having characteristic peaks at 7.6 ° and 28.6 ° in X-ray diffraction angle (2θ ± 0.2 °) with respect to u-Kα ray is dispersed in a resin. A single-layer dispersion type photoconductor characterized by the above. [Chemical 1] (In the general formula (1), the substituents R _{1 to} R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and = C (CN) ₂ . The substituent W is a ring having 4 to 8 membered rings, and when the above general formula (1) is rewritten as the following general formula (1 ′): The substituent Y is either an element of oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. ) 2. The compound of the general formula (1) is a compound of the general formula (2)
The single-layer dispersion type photoconductor according to claim 1, wherein [Chemical 3] (In the general formula (2), the substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 3. The compound of the general formula (1) is a compound of the general formula (3)
The single-layer dispersion type photoconductor according to claim 1, wherein [Chemical 4] (In the general formula (3), the substituents R _{1 to} R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 4. A compound represented by the following general formula (1), and C:
X-ray diffraction angle (2θ ± 0.2 °) for u-Kα ray is 2
A single-layer dispersion type photoconductor having a photosensitive layer in which oxytitanium phthalocyanine having a characteristic peak at 7.2 ° is dispersed in a resin. [Chemical 5] (In the general formula (1), the substituents R _{1 to} R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and = C (CN) ₂ . The substituent W is a ring having 4 to 8 membered rings, and when the above general formula (1) is rewritten as the following general formula (1 ′): The substituent Y is either an element of oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. ) 5. The compound of the general formula (1) is a compound of the general formula (2).
The single-layer dispersion type photoconductor according to claim 4, characterized by: [Chemical 7] (In the general formula (2), the substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 6. The compound of the general formula (1) is represented by the general formula (3).
The single-layer dispersion type photoconductor according to claim 4, characterized by: [Chemical 8] (In the general formula (3), the substituents R _{1 to} R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 7. A compound represented by the following general formula (1) and Cu
A single-layer dispersion type photosensitive material having a photosensitive layer in which oxytitanium phthalocyanine which does not show a characteristic peak at an X-ray diffraction angle (2θ ± 0.2 °) with respect to −Kα ray is dispersed in a resin. body. [Chemical 9] (In the general formula (1), the substituents R _{1 to} R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and = C (CN) ₂ . The substituent W is a ring having 4 to 8 membered rings, and when the above general formula (1) is rewritten to the following general formula (1 ′): The substituent Y is either an element of oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. ) 8. The compound of the general formula (1) is a compound of the general formula (2):
The single-layer dispersion type photoreceptor according to claim 7, which is represented by: [Chemical 11] (In the general formula (2), the substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 9. The compound of the general formula (1) is a compound of the general formula (3):
The single-layer dispersion type photoreceptor according to claim 7, which is represented by: [Chemical 12] (In the general formula (3), the substituents R _{1 to} R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 10. A single-layer dispersion type photoreceptor having a photosensitive layer in which a compound represented by the following general formula (1) and dichlorotin phthalocyanine are dispersed in a resin. [Chemical 13] (In the general formula (1), the substituents R _{1 to} R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and = C (CN) ₂ . The substituent W is a ring having 4 to 8 membered rings, and when the above general formula (1) is rewritten as the following general formula (1 ′): The substituent Y is either an element of oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. ) 11. The single-layer dispersion type photoreceptor according to claim 10, wherein the compound of the general formula (1) is represented by the general formula (2). [Chemical 15] (In the general formula (2), the substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 12. The single layer dispersion type photoreceptor according to claim 10, wherein the compound of the general formula (1) is represented by the general formula (3). [Chemical 16] (In the general formula (3), the substituents R _{1 to} R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 13. The dicyclorostuphthalocyanine is
X-ray diffraction angle (2θ ± 0.2 °) for Cu-Kα ray
11. The monolayer dispersion according to claim 10, wherein the maximum peak is at 10.5 °, and the peak intensity in the range of 5 ° to 9 ° is 10% or less of the peak intensity at 10.5 °. Type photoconductor. 14. A single-layer dispersion type photoreceptor having a photosensitive layer in which a compound represented by the following general formula (1) and a metal-free phthalocyanine are dispersed in a resin. [Chemical 17] (In the general formula (1), the substituents R _{1 to} R ₄ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and = C (CN) ₂ . The substituent W is a ring having 4 to 8 membered rings, and when the above general formula (1) is rewritten to the following general formula (1 ′): The substituent Y is either an element of oxygen or sulfur, and the structure Z is composed of two or more atoms constituting a ring. ) 15. The single-layer dispersion type photoreceptor according to claim 14, wherein the compound of the general formula (1) is represented by the general formula (2). [Chemical 19] (In the general formula (2), the substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. ) 16. The single layer dispersion type photoconductor according to claim 14, wherein the compound of the general formula (1) is represented by the general formula (3). [Chemical 20] (In the general formula (3), the substituents R _{1 to} R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, and a heterocyclic group. , An ester group, an alkoxy group, an aralkyl group,
Any one substituent selected from the group consisting of an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, and a carboxylic acid group. Is. The substituent X is oxygen,
It is any one kind of substituent selected from the group consisting of sulfur and ═C (CN) ₂ , and the substituent Y consists of either oxygen or sulfur. )