JP2001066809A - Electrophotographic photoreceptor, process cartridge with the same and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity and durability in the infrared region and to supply a stable image by using a gallium phthalocyanine compound as an electric charge generating material and an electric charge transferring compound having a specified structure as an electric charge transferring materiel. SOLUTION: The electrophotographic photoreceptor has a photosensitive layer containing at least one gallium phthalocyanine compound as an electric charge generating material and at least one compound of formula I as an electric charge transferring material. In the formula, Ar1 is aryl which may have a substituent, R1 is alkyl, aralkyl or aryl and R2 is an alkyl or aralkyl but Ar1 has at least one substituent of formula II, wherein R3 and R3 are each am alkyl which may have a substituent, aralkyl which may have a substituent, aryl which may have a substituent or H, R3 and R4 may be mutually the same or different, Ar2 is an aryl which may have a substituent and (n) is 0 or an integer of 1-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
More particularly, the present invention relates to an electrophotographic photosensitive member having a surface layer containing a specific resin, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art In electrophotography, U.S. Pat.
As shown in US Pat. No. 7,691, a photoconductive material whose electric resistance changes according to the irradiation dose received during image exposure and which is made of a support coated with an insulating material in a dark place is used. The basic characteristics required of an electrophotographic photoreceptor using this photoconductive material include (1) being able to be charged to an appropriate potential in a dark place, (2) having little charge dissipation in a dark place, and ( 3) Charge can be quickly dissipated by light irradiation.

Hitherto, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide or the like as a main component has been widely used. However, these satisfy the conditions (1) to (3), but are not necessarily satisfactory in heat stability, moisture resistance, durability, productivity, and the like. For example, selenium as a photoconductor is deteriorated by crystallization. Cadmium sulfide has a problem in moisture resistance and durability, and zinc oxide has a problem in smoothness, hardness and abrasion resistance. Furthermore, the photosensitive wavelength of many inorganic photosensitive members is limited. For example, the photosensitive wavelength region of selenium is the blue region, and the red region has little sensitivity.

Therefore, various methods have been devised to extend the photosensitivity to a long wavelength region, but there are many restrictions on the selection of the photosensitive wavelength region. Even when zinc oxide or cadmium sulfide is used as a photoreceptor, the photosensitive wavelength range of the photoreceptor itself is narrow, and it is necessary to add various sensitizers. In order to overcome the drawbacks of these inorganic photoconductors, electrophotographic photoconductors containing various organic photoconductive compounds as main components have been actively developed in recent years.

For example, US Pat. No. 3,837,851 discloses a photoreceptor having a charge transport layer containing triallylpyrazolin, and US Pat. No. 3,871,882.
The specification discloses a photoreceptor comprising a charge generation layer comprising a derivative of a perylene pigment and a charge transport layer comprising a condensate of 3-propylene and formaldehyde.

As an electrophotographic photoreceptor using an organic compound, a function-separated type electrophotographic photoreceptor classified into a charge generating substance for generating a charge and a charge transporting substance for transporting the charge is possible. The function-separated type photoreceptor has an advantage that a material selection range of a charge generating substance and a charge transporting substance is wide, and an electrophotographic photoreceptor having arbitrary characteristics can be relatively easily produced.

A photoreceptor using a bisazo pigment or a trisazo pigment as a charge generating substance is disclosed in JP-A-59-334.
No. 45, JP-A-56-46237, and JP-A-60-111249 are known.

Further, in the case of a photoreceptor using an organic photoconductive compound, the photosensitive wavelength of the electrophotographic photoreceptor can be freely selected depending on the compound. For example, with respect to azo organic pigments, some of the substances disclosed in JP-A-61-272754 and JP-A-56-167759 have high sensitivity in the visible light region. JP-A-57-195767 and JP-A-61-22845.
Some of the substances disclosed in Japanese Patent Publication No. 3 have sensitivity up to the infrared region.

Among these materials, those having sensitivity in the infrared region are used in laser beam printers (hereinafter abbreviated as LBPs), LED printers, and the like, which have been making remarkable progress in recent years, and their demands are increasing.

Apart from azo pigments, phthalocyanine compounds such as copper phthalocyanine as disclosed in JP-A-50-38543 have been attracting attention as those having sensitivity in the infrared region. Particularly, in recent years, materials having high sensitivity in the infrared region are disclosed in JP-A-61-2705, JP-A-61-239248, and JP-A-64-17066.
And oxytitanium phthalocyanine compounds disclosed in Japanese Patent Application Laid-Open No. Hei.

Further, in the case of the gallium phthalocyanine compound used in the electrophotographic photoreceptor of the present invention, for example, a chlorogallium phthalocyanine compound is disclosed in
1459, JP-A-5-98181, JP-A-5-194523, JP-A-5-247361, JP-A-6-73303, JP-A-7-5389
No. 1 and JP-A-7-207171, etc., and as a hydroxygallium phthalocyanine compound,
JP-A-5-236007, JP-A-5-27959
No. 1, JP-A-6-93203, JP-A-6-2
79698 and JP-A-7-53892.

The charge transport material which is another component of the function-separated type photoreceptor will be described. For example, pyrazoline compounds described in JP-B-52-4188, etc.
JP-B-55-42380, JP-A-54-1501
No. 28, JP-A-57-101844 and JP-A-7-152187, hydrazone compounds, JP-B-58-32372 and JP-A-61-12395.
JP-A-5-54, etc .;
Stilbene compounds and the like disclosed in JP-A-151955 and JP-A-58-198043 are known.

Examples of combinations of these charge generating substances and charge transport substances include the combination of oxytitanium phthalocyanine and a hydrazone compound having a specific structure disclosed in JP-A-5-55860.
9716, JP-A-5-257310, JP-A-6-75408, JP-A-6-324502, JP-A-7-84390 and JP-A-8-54
No. 744 discloses a combination of hydroxygallium phthalocyanine or chlorogallium phthalocyanine with a charge transport compound having a specific structure.

Although a photoreceptor having improved characteristics by combining a charge generating material having a specific structure and a charge transporting material having a specific structure has been supplied, high sensitivity in the infrared region is not always required. However, the potential stability during repeated use is poor, the charging ability is poor, and image deterioration due to a change in the use environment is observed.

In the case of an apparatus employing a reversal development system compatible with digitization for the above-mentioned applications such as LBP, primary charging and transfer have opposite polarities, and the chargeability differs depending on the presence or absence of transfer. Memory is generated, and it is very easy to appear as uneven density on an image.

Further, in the electrophotographic photosensitive member with high sensitivity, a so-called photo memory, in which the chargeability of a bright portion and a dark portion is different due to external leakage light or the like, occurs, which also causes density unevenness on an image. It is very easy to appear.

As described above, there are some problems in practical use, and it is hard to say that a photoconductor which achieves these characteristics at a high level has been supplied yet. Electrophotographic photoreceptors satisfying a higher level have been studied.

In general, in an electrophotographic photoreceptor, a charge transporting substance which is very effective for a specific charge generating substance is not always as effective as another charge generating substance. Conversely, a charge generation material that is very effective for one particular charge transport material is not always as effective for another charge transport material. That is, there is always a more preferable combination between the charge generating material and the charge transporting material that transfer charges.

When a more preferable combination of the charge generating substance and the charge transporting substance is used, it is possible to obtain an electrophotographic photosensitive member having more excellent characteristics in terms of residual potential, potential stability upon repeated use, and the like.

However, no general rule has been found for the compatibility between the charge generating substance and the charge transporting substance.
It is very difficult at present to predict the optimal charge transport material for a particular charge generating material.

[0021]

SUMMARY OF THE INVENTION The present invention provides an organic photoconductive compound which sufficiently satisfies the characteristics required for the above-mentioned electrophotographic photoreceptor, thereby solving various disadvantages of the conventional electrophotographic photoreceptor. The task is to eliminate it. That is, (1) to provide an electrophotographic photoreceptor having a sufficiently high sensitivity in a long wavelength region, (2) to maintain a stable electric potential during repeated use, and (3) to provide a temperature and humidity environment. (4) To provide an electrophotographic photosensitive member that does not easily generate a transfer memory even in a reversal developing system; (5) To provide a light-resistant and photo memory It is an object to provide an electrophotographic photosensitive member that is difficult to obtain.

Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[0023]

The present inventors have conducted a number of experimental studies on combinations of various charge generating substances and charge transporting substances. As a result, the present inventors have found that a gallium phthalocyanine compound is used as the charge generating substance, When a charge transport compound having a specific structure such as the general formulas (1) and (3) of the present invention is combined, the compound has high sensitivity and durability in the infrared region, and is stable even in various environments. The present inventors have found that a photoreceptor for supplying a prepared image can be produced, and have reached the present invention.

Further, among the gallium phthalocyanine compounds, the case of a chlorogallium phthalocyanine compound or a hydroxygallium phthalocyanine compound is particularly preferred.

The gallium phthalocyanine compound of the present invention,
Among them, the reason why a combination of a chlorogallium phthalocyanine compound or a hydroxygallium phthalocyanine compound and a charge transport compound having a specific structure as represented by the general formulas (1) and (3) of the present invention is not clear is unknown, but the ionization potential is not clear. Because the charge is injected from the charge generating substance to the charge transporting substance satisfactorily because of conformity or good steric overlap when the charge generating substance and the charge transporting substance are mixed, the sensitivity is good and the residual potential is also low. It is presumed that it is small, has excellent potential stability during repeated use, and also has excellent properties such as various memories.

According to the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains at least one kind selected from a gallium phthalocyanine compound as a charge generating substance, and has a charge transport property. As a substance, the following general formula (1)

[0027]

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[In the formula, Ar ¹ represents an aryl group which may have a substituent; R ¹ represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent R ² represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent; provided that Ar ¹ represents the following general formula (2) [Formula 5]

[0029]

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(Wherein R ³ and R ⁴ each represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. R ³ and R ⁴ may be the same or different; Ar ² represents an aryl group which may have a substituent; n represents 0 or an integer of 1 to 2) R ¹ and R ² or R ¹ and Ar ¹ or Ar ² and R ⁴ may form a ring directly or via another organic residue. An electrophotographic photosensitive member comprising at least one compound represented by the formula:

According to another aspect of the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains at least one selected from a gallium phthalocyanine compound as a charge generating substance, and The following general formula (3) is used as the charge transport material.

[0032]

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(Wherein, Ar ₃ and Ar ₄ each represent an arylene group which may have a substituent; R ₅ , R ₇ and R ₈ each represent an alkyl group which may have a substituent, R ₆ represents an aralkyl group which may have a substituent or an aryl group which may have a substituent; R ₆ represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent; n represents 0 or 1; R ₅ and R ₇ or R ₅ and A
r ₃ or Ar ₄ and R ₇ or Ar ₃ and Ar ₄ may form a ring directly or via another organic residue. An electrophotographic photosensitive member comprising at least one compound represented by the formula (1):

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The electrophotographic photoreceptor of the present invention contains at least one gallium phthalocyanine compound as a charge generating substance in the photosensitive layer, and preferably contains at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound. Among them, those having several crystal types as shown below exhibit more preferable characteristics of the present invention.

The chlorogallium phthalocyanine compound is
It is composed of a crystalline pigment having a Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα having strong peaks at 7.4 °, 16.6 °, 25.5 °, and 28.2 °.

The chlorogallium phthalocyanine compound is
The Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα is 8.7 ° to 9.2 °, 17.5 °, 24.0 °, 2
It consists of a crystalline pigment with strong peaks at 7.4 ° and 28.7 °.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2% is composed of a crystalline pigment having strong peaks at 6.8 ° and 26.2 °.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2% is composed of a crystalline pigment having strong peaks at 7.4 ° and 28.2 °.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2 ゜ is 7.5 ゜, 16.3 ゜, 24.9 ゜ and 26.4
゜ is composed of a crystalline pigment having a strong peak.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2 ゜ is 6.9 ゜, 13.3 ゜, 16.5 ゜ and 26.7
゜ is composed of a crystalline pigment having a strong peak.

Next, the electrophotographic photoreceptor of the present invention contains a specific styryl compound represented by the general formula (1) as a charge transporting substance. In the general formula (1), R ¹
Is preferably an aryl group which may have a substituent, and more preferably, in the general formula (2), R ⁴ is an aryl group which may have a substituent. Or even
In the general formula (2), n is more preferably 0.

The aryl groups represented by the above formulas (1) and (2) include aromatic hydrocarbon groups such as phenyl, naphthyl, anthracenyl and pyrenyl, pyridyl,
Examples include heterocyclic groups such as quinolyl, thienyl, furyl, carbazolyl, benzimidazolyl, and benzothiazolyl. Examples of the alkyl group include methyl, ethyl, propyl,
Groups such as butyl and hexyl. Examples of the aralkyl group include groups such as benzyl, phenethyl, naphthylmethyl, and furfuryl.

Examples of the substituent which these groups may have include alkyl groups such as methyl, ethyl, propyl, butyl and hexyl, alkoxy groups such as methoxy, ethoxy and butoxy, and aryloxy groups such as phenoxy and naphthoxy. Groups, halogen atoms such as fluorine, chlorine, bromine and iodine,
Aromatic hydrocarbon groups such as phenyl and naphthyl, pyridyl,
Heterocyclic groups such as quinolyl, thienyl and furyl, acetyl,
Acyl groups such as benzyl, alkylamino groups such as dimethylamino, haloalkyl groups such as trifluoromethyl,
Examples include a cyano group, a nitro group, a phenylcarbamoyl group, a carboxyl group, and a hydroxyl group. When R ¹ is an aryl group, R ¹ may have a substituent represented by the general formula (2) in addition to the above substituent.

Incidentally, R ¹ and R ² or R ² and Ar ¹ or Ar ² and R ⁴ can be directly or other —CH ₂ —, —CH ₂ C
A ring may be formed via an organic residue such as H ₂ —, —CH ＝ CH—, —O—, and —S—.

The effect of the present invention is such that an excellent effect is selectively exhibited only when the above-mentioned specific charge generating substance and the specific charge transporting substance are used in combination.

Next, specific examples of the compound represented by the general formula (1) are shown in Tables 1 to 3 below. However, it is not limited to these specific examples.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

Next, the electrophotographic photoreceptor of the present invention contains a specific charge transport compound represented by the general formula (3) as a charge transport material. In the general formula (3), Ar ₃
And Ar ₄ is preferably a phenylene group which may have a substituent. Further, when n = 0 in the general formula (3), R ₅ is an aryl group which may have a substituent, and n = 1
In the case of R ₅ and R ₇ are more preferably an aryl group which may have a substituent.

The arylene group represented by the general formula (3) includes benzene, naphthalene, anthracene,
Examples thereof include groups obtained by removing two hydrogen atoms from a heterocyclic ring such as an aromatic hydrocarbon such as pyrene or the like, pyridine, thiophene, quinoline, and furan. Examples of the aryl group include aromatic hydrocarbon groups such as phenyl, naphthyl, anthracenyl, and pyrenyl; and heterocyclic groups such as pyridyl, quinolyl, thienyl, furyl, carbazolyl, benzimidazolyl, and benzothiazolyl. Examples of the alkyl group include groups such as methyl, ethyl, propyl, butyl, and hexyl.
Examples of the aralkyl group include groups such as benzyl, phenethyl, naphthylmethyl, and furfuryl.

Examples of the substituent which these groups may have include alkyl groups such as methyl, ethyl, propyl, butyl and hexyl, alkoxy groups such as methoxy, ethoxy and butoxy, and aryloxy groups such as phenoxy and naphthoxy. Groups, halogen atoms such as fluorine, chlorine, bromine and iodine,
Aromatic hydrocarbon groups such as phenyl and naphthyl, pyridyl,
Heterocyclic groups such as quinolyl, thienyl and furyl, acetyl,
Examples include acyl groups such as benzyl, alkylamino groups such as dimethylamino and diethylamino, haloalkyl groups such as trifluoromethyl, cyano group, nitro group, phenylcarbamoyl group, carboxyl group, and hydroxyl group.

Note that R_FiveAnd R₆Or R_FiveAnd Ar_ThreeOr
Ar_FourAnd R₇Or Ar_ThreeAnd Ar_FourIs directly or other-
CR₉R_Ten-, -CH_TwoCH_Two-, -CH = CH-,-
O-, -S-, -NR₁₁-Form a ring via an organic residue such as
May be implemented. Note that R₉, R _TenAnd R₁₁Is a hydrogen atom
Or alkyl such as methyl, ethyl, propyl, butyl, etc.
And aralkyl groups such as benzyl and phenethyl.

The effect of the present invention is such that an excellent effect is selectively exhibited only when the specific charge generating substance and the specific charge transporting substance are used in combination.

Next, specific examples of the compound represented by the general formula (3) are shown in Tables 4 to 10 below. However, it is not limited to these specific examples.

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

[Table 8]

[0061]

[Table 9]

[0062]

[Table 10]

Among the gallium phthalocyanine compounds used in the present invention, a particularly preferred structure of a chlorogallium phthalocyanine compound is represented by the following general formula (4) [formula 7], and a structure of hydroxygallium phthalocyanine is represented by the following general formula (5) It is shown in [Formula 8].

[0064]

Embedded image

However, X _4-1 , X _4-2 , X _4-3 and X
_4-4 represents Cl or Br, and n ₄ , m ₄ , l ₄ and k
₄ is an integer of 0-4.

[0066]

Embedded image

Similarly, X _5-1 , X _5-2 , X _5-3 and X
_5-4 represents Cl or Br, and n ₅ , m ₅ , l ₅ and k
₅ is an integer of 0-4.

Next, production examples of the charge generating substance and the charge transporting substance used in the present invention will be described below. However, the present invention is not limited to these production examples. Hereinafter, the unit “parts” indicates parts by weight.

[Production Example 1] Production of chlorogallium phthalocyanine 72.6 g of o-phthalonitrile, 25 gallium trichloride
g, 375 ml of α-chloronaphthalene in a nitrogen atmosphere 2
The reaction was performed at 00 ° C. for 4 hours. After the reaction, the precipitated product was cooled to 130 ° C. and filtered. The product obtained is N,
The resultant was dispersed and washed with N-dimethylformamide at 130 ° C. for 1 hour, and filtered. After washing with a filter using methanol, the precipitate was dried under reduced pressure to obtain 39.8 g of chlorogallium phthalocyanine (yield: 45%). The results of elemental analysis of the obtained chlorogallium phthalocyanine are shown below. The infrared absorption spectrum of this crystal (KBr tablet method) is shown in FIG.
FIG. 2 shows a powder X-ray diffraction pattern.

[0070] [Production Example 2] Production of chlorogallium phthalocyanine Next, 30 parts of the chlorogallium phthalocyanine obtained in Production Example 1 was subjected to dry milling for 24 hours in a ball mill together with 100 parts of an agate ball of 10 mmφ and 200 parts of an agate ball of 20 mmφ. . Next, 7 parts of the milled crystal and 280 parts of benzyl alcohol were added to 1 part.
Milling treatment was performed for 20 hours at room temperature (22 ° C.) with a sand mill together with 420 parts of the glass beads having a diameter of mm. The pigment was separated from this dispersion by filtration, washed with methanol, and dried under reduced pressure, so that the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα was 7.4 °, 16.6 °, 25.
Crystalline chlorogallium phthalocyanine having strong peaks at 5 ° and 28.2 ° was obtained. FIG. 3 shows a powder X-ray diffraction pattern of the crystals.

[Production Example 3] Production of chlorogallium phthalocyanine 7 parts of chlorogallium phthalocyanine crystals and 280 parts of methanol, which were dry-milled in the same manner as in Production Example 2, were mixed for 1 m.
Milling treatment was performed for 20 hours at room temperature (22 ° C.) with a sand mill together with 420 parts of mφ glass beads. The pigment is separated from this dispersion by filtration and dried under reduced pressure, whereby C
Bragg angles 2θ ± 0.2 ° in X-ray diffraction of uKα are 8.7 ° to 9.2 °, 17.5 °, 24.0 °, 27.
Crystalline chlorogallium phthalocyanine having strong peaks at 4 ° and 28.7 ° was obtained. FIG. 4 shows a powder X-ray diffraction pattern of this crystal.

[Production Example 4] Production of hydroxygallium phthalocyanine Chlorogallium phthalocyanine 35 obtained in Production Example 1
g was gradually added to and dissolved in 1050 g of concentrated sulfuric acid cooled to 0 ° C., followed by stirring at 0 ° C. for 30 minutes. Then ice water 5250
The resulting solution was slowly dropped into the resulting solution while stirring to cause reprecipitation. After reprecipitation, filtration was performed, and the obtained powder was dispersed and washed in 2500 g of ion-exchanged water, and filtered again. Further, the obtained powder is
The solid obtained by dispersing and washing in 2500 g of aqueous ammonia and further thoroughly washing with ion-exchanged water was dried under reduced pressure. 33.9 g of low crystalline hydroxygallium phthalocyanine was obtained (yield: 97%). The results of elemental analysis of the obtained hydroxygallium phthalocyanine are shown below. FIG. 5 shows an infrared absorption spectrum (KBr tablet method) of the crystal, and FIG. 6 shows a powder X-ray diffraction pattern.

[0073] [Production Example 5] Production of hydroxygallium phthalocyanine Next, 7 parts of hydroxygallium phthalocyanine obtained in Production Example 4 and N, N-dimethylformamide 21
0 parts were milled by a sand mill together with 300 parts of 1 mmφ glass beads at room temperature (22 ° C.) for 5 hours.
The pigment was separated from the dispersion by filtration, washed with methanol, and dried under reduced pressure, whereby the Bragg angles 2θ ± 0.2 ° in X-ray diffraction of CuKα were strong peaks at 7.4 ° and 28.2 °. The crystal form hydroxygallium phthalocyanine having the following formula was obtained. FIG. 7 shows a powder X-ray diffraction pattern of this crystal.

[Production Example 6] Production of hydroxygallium phthalocyanine Next, 7 parts of the hydroxygallium phthalocyanine obtained in Production Example 4 and 210 parts of methanol were milled together with 300 parts of 1 mmφ glass beads by a sand mill at room temperature (22 ° C.). Performed for 5 hours below. The pigment is filtered off from the dispersion and dried under reduced pressure to obtain X of CuKα.
Bragg angle 2θ ± 0.2 ° in X-ray diffraction is 7.5 °,
Crystalline hydroxygallium phthalocyanine having strong peaks at 16.3 °, 24.9 ° and 26.4 ° was obtained. FIG. 8 shows a powder X-ray diffraction pattern of this crystal.

[Production Example 7] Production of hydroxygallium phthalocyanine Next, 7 parts of the hydroxygallium phthalocyanine obtained in Production Example 4 and 210 parts of chloroform were milled by a sand mill together with 300 parts of 1 mmφ glass beads at room temperature (22 ° C.). Performed for 5 hours below. The pigment was separated from this dispersion by filtration and dried under reduced pressure, so that the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα was 6.9.
Crystalline hydroxygallium phthalocyanine having strong peaks at {, 13.3}, 16.5 ° and 26.7 ° was obtained. FIG. 9 shows a powder X-ray diffraction pattern of this crystal.

The chlorogallium phthalocyanine compound and hydroxygallium phthalocyanine compound of the present invention can be produced as described above, but are not limited to these production examples.

The typical layer constitution of the electrophotographic photosensitive member of the present invention includes the following forms. Figure 1 is a schematic diagram
0 and FIG. FIG. 10 shows that the photosensitive layer 10-1 simultaneously contains the charge generating substance 10-2 and the charge transporting substance (not shown). In addition, 10-3 is a conductive support.

FIG. 11 shows that the photosensitive layer 11-1 is the charge generation layer 11
-4 and a charge transport layer 11-5. The charge generation layer 11-4 contains a charge generation material 11-2, and the charge transport layer 11-5 contains a charge transport material (not shown). Contains. Note that the stacking relationship between the charge generation layer 11-4 and the charge transport layer 11-5 in FIG. 11 may be reversed. 11-
3 is a conductive support.

In the electrophotographic photoreceptor of the present invention, the charge generation layer contains as much charge generation substance as possible in order to obtain a sufficient absorbance, and in order to shorten the range of the generated charge carrier. It is desirable to form a thin film layer having a thickness of 5 μm or less, preferably a thin film layer having a thickness of 0.01 to 1 μm.

The charge generation layer can be formed by dispersing a charge generation substance in an appropriate binder and applying the same to a conductive support.

The binder used when forming by coating can be selected from a wide range of insulating resins, and can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. Preferably, polyvinyl butyral, polyarylate (polycondensate of bisphenol and aromatic dicarboxylic acid), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinyl pyridine, cellulose resin, polyurethane, epoxy Resins, casein, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be mentioned.
The content in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less of the resin.

The solvent for dissolving these resins differs depending on the type of the resin, and is preferably selected from the types that do not dissolve the charge transport layer or the undercoat layer. Specifically, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexane, N, N-dimethylformamide, N, N
-Amides such as dimethylacetamide, sulfoxides such as dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethylene, carbon tetrachloride And aromatic halogenated hydrocarbons such as trichloroethylene or aromatic compounds such as benzene, toluene, xylene, ligroin, chlorobenzene and dichlorobenzene.

As a coating method, a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a Meyer bar coating method, a blade coating method, a roller coating method, a carting method, or the like can be adopted. Drying is preferably performed by drying at room temperature and then heating and drying. Heat drying is 3
It is carried out in a temperature range of 0 to 200 [deg.] C. for 5 minutes to 2 hours under static or blast.

The charge transport layer is electrically connected to the charge generation layer, and has a function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. are doing. At this time, the charge transport layer may be stacked on the charge generation layer, or may be stacked thereunder.

The charge transport layer can be formed by dissolving a compound having a specific structure represented by the general formulas (1) and (3) together with a suitable binder, and applying the resulting solution.

Examples of the binder resin include insulating resins such as acrylic resin, polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, and chlorinated rubber. And organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. Since the charge transport layer has a limit for transporting charge carriers, it cannot be made thicker than necessary, but 3 to 50 μm, preferably 8 to 50 μm.
30 μm. When forming the charge transport layer by coating, the above-mentioned appropriate coating method can be adopted.

An electrophotographic photosensitive member having a laminated structure of a charge generation layer and a charge transport layer is provided on a conductive support.

As the conductive support, those having conductivity itself, for example, metals and alloys such as aluminum and aluminum alloys are used. In addition, aluminum, aluminum alloys, indium oxide, tin oxide, indium oxide-oxide A plastic having a layer formed by a vacuum deposition method using a tin alloy or the like, a conductive support in which conductive particles (eg, carbon black, silver particles, etc.) are coated on a plastic or the metal support with a suitable binder, A conductive support in which conductive particles are impregnated in plastic or paper, a plastic having a conductive polymer, or the like is used.

A layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer. The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc. . The thickness of the undercoat layer is 0.1 to 5 μm, preferably 0.1 to 5 μm.
5 to 3 μm.

The electrophotographic photoreceptor of the present invention may be provided with a surface protective layer, if necessary.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
RT printer, LED printer, LCD printer,
It can be widely used in electrophotographic applications such as laser plate making and facsimile.

FIG. 12 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 12, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member, which is driven to rotate around an axis 2 in a direction indicated by an arrow at a predetermined peripheral speed. In the rotation process, the photosensitive member 1 is uniformly charged around the periphery thereof by the primary charging means 3 at a predetermined positive or negative potential, and then exposed light from exposure means (not shown) such as slit exposure or laser beam scanning exposure. Receive 4. Thus, an electrostatic latent image is sequentially formed around the photoconductor 1.

The formed electrostatic image is then developed.
The toner-developed image thus developed is transferred from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed to a transfer material 7 fed therefrom.
The image is sequentially transferred by the transfer unit 6.

The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy out of the apparatus.

After the transfer of the image, the surface of the photoreceptor 1 is cleaned by removing the untransferred toner by a cleaning unit 9 and further subjected to a charge removal process by a pre-exposure light 10 from a pre-exposure unit (not shown). , Which are used repeatedly for image formation.
When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, a process in which at least one of the primary charging unit 3, the developing unit 5 and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and is detachably attached to the apparatus main body using a guide unit such as the rail 12 of the apparatus main body. The cartridge 11 can be used.

When the electrophotographic apparatus is a copier or a printer, the exposure light 3 is reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and a laser beam is emitted in accordance with the signal. This is light emitted by scanning a beam, driving an LED array, driving a liquid crystal shutter array, and the like.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
It can be widely used in electrophotographic applications such as RT printers, LED printers, liquid crystal printers, and laser plate making.

[0100]

EXAMPLES Next, the combination of the charge generating substance and the charge transporting substance of the present invention will be described based on actually performed examples and comparative examples. However, the present invention is not limited to these examples. The charge generation materials used in Examples and Comparative Examples are shown in Tables 11 and 12 below.

[0101]

[Table 11]

[0102]

[Table 12]

Example 1 0.42 μm on an aluminum substrate
An undercoat layer comprising a vinyl chloride-maleic anhydride-vinyl acetate copolymer was formed. Next, 4 parts of a hydroxygallium phthalocyanine compound having a crystal form of Pigment No. P-4 shown in Table 11 and 2 parts of a polyvinyl butyral resin (butyralization degree: 65 mol%, number average molecular weight: 35,000) were added to 80 parts of cyclohexanone. The mixture was dispersed with glass beads for 4 hours in a sand mill, and diluted with 80 parts of ethyl acetate. This was applied on a subbing layer with a Meyer bar so that the film thickness after drying was 0.24 μm, and charge was generated. A layer was formed.

Next, the exemplary compound N as a charge transport material
o. 14 and 4.5 parts of bisphenol Z-type polycarbonate (viscosity average molecular weight 20,000) were dissolved in 38 g of monochlorobenzene, and this solution was applied on a charge generating layer with a Meyer bar so that the film thickness after drying was 23 μm. And
After drying, a charge transport layer was formed. 1 was produced.

This photoreceptor was affixed to a cylinder of a modified machine of a laser beam printer (Laser Jet 4000: manufactured by Hewlett-Packard), and was exposed to normal dark area potential (N / N) under normal temperature and normal humidity (23 ° C., 55% RH) (N / N). Vd) is set to be -700 (V).
This was irradiated with a laser beam having a wavelength of 780 (nm) to obtain -7.
00 the potential of (V) was measured sensitivity required amount (EΔ ₅₀₀₎ to lower to -200 (V). In addition, 20
The initial characteristics were measured by setting the potential when a light amount of (μJ / cm ² ) was irradiated as the residual potential (Vr). The other conditions were as follows: transfer current: +5.5 μA, process speed: 9
The measurement was performed at 6 mm / sec.

Thereafter, the environment was changed to high temperature and high humidity (32 ° C., 85%
RH) (H / H), and the amount of change (ΔVl) of Vl from room temperature and normal humidity was measured.

Next, the photoconductor No. 1 was newly prepared by the same method as described above. 1 was attached to the cylinder of a remodeling machine similar to the above, and at room temperature and low humidity (23 ° C., 10% RH) (N /
L), the continuous running of 2,000 sheets is performed, and the fluctuation amounts of the dark portion potential and the bright portion potential at the initial stage and immediately after the endurance are ΔVd ¹ and ΔVl.
¹ was measured.

Further, the transfer memory and the photo memory were measured as follows.

The measurement of the transfer memory is newly performed as described above.
The electrophotographic photoreceptor manufactured by the method of
Transfer current OFF with N / N after pasting on machine cylinder
The primary charging potential is Vd^Two, Primary charging when transfer current is ON
Potential Vd^ThreeAs | Vd ^Two-Vd^Three| Was measured.

Further, as a measurement of a photo memory with respect to white light, an electrophotographic photosensitive member newly produced by the same method as described above was attached to a cylinder of a modified machine similar to the above, and the initial dark area potential (N / N) was measured. Vd) / initial light portion potential (V
1) The charging and the image exposure light amount are set so that -700 (V) /-200 (V) is obtained. Then, the electrophotographic photosensitive member is masked so that a dark portion and a bright portion are formed, and the electrophotographic photoreceptor is exposed under a fluorescent lamp. After irradiating with light at 3000 lux for 20 minutes, the sample was left for 5 minutes, and the potential was measured in the same manner. The absolute value (ΔVd ⁴ ) of the change from the initial value of the dark portion potential was measured as a photo memory. The above results are shown in Table 13 below.

[Examples 2] to [30] [0111] Except that the pigment and / or the charge transporting substance of Example 1 were changed as shown in Tables 13 to 14 below as the charge generating substance, An electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the same evaluation was performed. Tables 13 and 14 show the results.

[0112]

[Table 13]

[0113]

[Table 14]

[Comparative Examples 1 to 30] The pigment and / or the charge transporting material of Example 1 were used as the charge generating material in Table 1 below.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the results were changed as shown in Tables 5 to 16. Tables 15 and 16 show the results.

[0115]

[Table 15]

[0116]

[Table 16]

The structure of the comparative charge transporting material is as follows (H
-9) The compounds shown in [Formula 9] to (H-16) [Formula 16] were used.

[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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As is clear from the results of Tables 13 to 16, the chlorogallium phthalocyanine compound and the hydroxygallium phthalocyanine compound as the charge generating materials indicated by the present invention and the general formula (1) as the charge transporting material
The electrophotographic photoreceptor in which a styryl compound having a specific structure represented by the following formula is combined has high sensitivity, low residual potential, extremely small potential fluctuation in various environments, and has stable characteristics. Further, it is clear that transfer memory, photo memory, and the like also exhibit extremely small and excellent characteristics.

Example 31 An undercoat layer similar to that of Example 1 was formed on an aluminum sheet substrate having a thickness of 50 μm by bar coating, and a charge transport layer similar to that of Example 1 was further formed thereon with a thickness of 18 μm. Formed.

Next, 6 parts of bisphenol Z-type polycarbonate was dissolved in 66 parts of cyclohexanone, and 4.0 parts of hydroxygallium phthalocyanine of pigment No. P-4 shown in Table 11 was mixed with the solution, and dispersed in a sand mill for 10 hours. After that, bisphenol Z-type polycarbonate 5
And 9.5 parts of the charge transport material used in Example 1 were dissolved, and 40 parts of tetrahydrofuran and 4 parts of dichloromethane were dissolved.
0 parts were added and diluted to obtain a dispersion paint. This paint is applied on the charge transport layer by a spray coating method and dried to 6 μm
To form an electrophotographic photoreceptor (Example photoreceptor No. 31).

Example 32 The procedure of Example 31 was repeated except that chlorogallium phthalocyanine having a crystal form of pigment number P-1 shown in Table 11 was used instead of the pigment number P-4 of Example 31 as the charge generating material. An electrophotographic photosensitive member (working photosensitive member No. 32) was produced in the same manner as in Example 31.

[Comparative Example 31] A comparative pigment number Q-1 (τ-type metal-free phthalocyanine) shown in Table 12 was used in place of the pigment number P-4 of Example 31 as the charge generating substance. An electrophotographic photoreceptor (comparative photoreceptor No. 31) was produced in the same manner as in Example 31.

Comparative Example 32 The procedure of Example 31 was repeated except that Comparative Pigment No. Q-2 (ε-copper phthalocyanine) shown in Table 12 was used in place of Pigment No. P-4 of Example 31 as the charge generating material. An electrophotographic photoreceptor (comparative photoreceptor No. 32) was produced in the same manner as in Example 31.

[Comparative Example 33] A comparative pigment number Q-3 (β-type oxytitanium phthalocyanine) shown in Table 12 was used in place of the pigment number P-4 of Example 31 as the charge generating substance. An electrophotographic photosensitive member (comparative photosensitive member No. 33) was produced in the same manner as in Example 31.

[Comparative Example 34] Instead of the pigment number P-4 of Example 31, the comparative pigment number Q-4 (the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα) shown in Table 12 was used instead of the pigment number P-4 of Example 31. An electrophotographic photoreceptor (Example photoreceptor No. 34) was prepared in the same manner as in Example 31 except that oxytitanium phthalocyanine having peaks at 9.6 ° and 27.2 °) was used.

The thus obtained electrophotographic photosensitive members of Examples 31 and 32 and Comparative Examples 31 to 34 were each used in an electrostatic tester (EP
A-8100: manufactured by Kawaguchi Electric Co., Ltd.).

In the evaluation, first, the surface potential was set to +700 (V) by positive corona charging, and then the surface potential was lowered to +200 (V) by exposure to monochromatic light of 802 nm which was separated by a monochromator. The amount of light at that time was measured and used as sensitivity. Table 17 shows the results.

[0136]

[Table 17]

Example 33 N-methoxymethylated 6 nylon resin (weight average molecular weight 4500) was placed on an aluminum substrate.
0) 4.2 parts and 8.8 parts of alcohol-soluble copolymerized nylon resin (weight average molecular weight: 50,000)
The solution dissolved in 0 part was applied with a Meyer bar, and an undercoat layer having a thickness of 0.6 μm after drying was provided.

As charge generation substances, 12 parts of pigment number P-4 hydroxygallium phthalocyanine shown in Table 11, 10 parts of polyvinyl butyral resin (butyralization ratio: 65%, weight average molecular weight: 45,000) and 200 parts of cyclohexanone
Was dispersed for 24 hours using a ball mill disperser. This dispersion was applied on the undercoat layer prepared previously by a blade coating method to prepare a charge generation layer having a dried film thickness of 0.22 μm.

Next, the exemplified compound No. 75 to 5.0
Part and No. 4.5 parts of 78 and 10 parts of polyarylate resin (weight average molecular weight: 50,000) are dissolved in 70 parts of monochlorobenzene, coated on the charge generation layer prepared previously by a blade coating method, and dried to obtain a film thickness. 18 μm
Was produced.

The photoreceptor thus produced was applied with a voltage of -5 kV.
Was subjected to corona discharge. At this time, the surface potential (initial potential V0) was measured. Further, the surface potential of this photoreceptor when left in a dark place for 1 second was measured. The sensitivity is the exposure amount (E) required to attenuate the potential (V1) after dark decay to 1/5.
_1/5 : μJ / cm ² ). At this time, a quaternary semiconductor laser of indium / gallium / aluminum / phosphorus (output: 5 mW;
An oscillation wavelength of 680 nm) was used. The results were as follows.

V0: -700 (V) V1: -695 (V) E _1/5 : 0.32 (μJ / cm ² ) Next, a reversal developing type electrophotographic printer equipped with a semiconductor laser as described above. The photosensitive member was attached to a laser beam printer (LBP-SX manufactured by Canon Inc.), and an actual image forming test was performed. The conditions are as follows.

Surface potential of primary charge: -700 (V) Surface potential of image exposure: -150 (V) Transfer potential: +700 volts Development polarity: negative polarity Process speed: 50 (mm / sec) Development condition (development bias) : -450 (V) Image exposure scan method: Image scan Exposure before primary charging: 50 (lux / sec) full red exposure Image formation was performed by line scanning laser beam according to character signals and image signals. Good prints were obtained for both images.

Further, when 5000 images were continuously printed, stable prints were obtained from the initial stage to 5000 sheets.

[Embodiment 34] 0.42 μm on an aluminum substrate
An undercoat layer composed of a vinyl chloride-maleic anhydride-vinyl acetate copolymer was formed. Next, 5 parts of a hydroxygallium phthalocyanine compound having a crystal form of Pigment No. P-4 shown in Table 11 and a polyvinyl butyral resin (butyralization degree: 68 mol%, number average molecular weight: 30,000) 2
Was added to 80 parts of cyclohexanone, dispersed in a sand mill with glass beads for 10 hours, diluted with 80 parts of ethyl acetate, and dried on an undercoat layer so that the film thickness after drying was 0.2 μm. Was applied with a Meyer bar to form a charge generation layer. Next, Exemplified Compound No. 1 was used as a charge transport material. 4.5 parts of 51 and 5 parts of bisphenol Z-type polycarbonate (viscosity average molecular weight 20,000) are dissolved in 38 g of monochlorobenzene, and this solution is applied on a charge generation layer by a Meyer bar so that the film thickness after drying becomes 20 μm. And dried to form a charge transport layer. Three
4 was produced.

This photoreceptor was attached to a cylinder of a modified machine of a laser beam printer (Laser Jet 4000: manufactured by Hewlett-Packard), and the initial dark area potential (N / N) under normal temperature and normal humidity (23 ° C., 55% RH) (N / N). Vd) is set to be -700 (V).
This was irradiated with a laser beam having a wavelength of 780 (nm) to obtain -7.
00 the potential of (V) was measured sensitivity required amount (EΔ ₅₀₀₎ to lower to -200 (V). In addition, 20
The initial characteristics were measured by setting the potential when a light amount of (μJ / cm ² ) was irradiated as the residual potential (Vr). The other conditions were as follows: transfer current: +5.5 μA, process speed: 9
The measurement was performed at 6 mm / sec.

Thereafter, the environment was changed to high temperature and high humidity (32 ° C., 85%
RH) (H / H), and the amount of change (ΔV1) of V1 from normal temperature and normal humidity was measured.

Next, the photoconductor No. 1 was newly prepared in the same manner as described above. 34 is attached to the cylinder of a remodeling machine similar to the above, and is placed under normal temperature and low humidity (23 ° C., 10% RH) (N
/ L), the continuous paper passing durability of 2,000 sheets is performed, and the fluctuation amounts (ΔVd ¹ and ΔVd ¹⁾ of the dark portion potential and the bright portion potential at the initial stage and immediately after the endurance.
l ¹ ) was measured.

Further, the measurement of the transfer memory and the photo memory was performed as follows.

The measurement of the transfer memory is newly performed as described above.
The electrophotographic photoreceptor manufactured by the method of
Transfer current OFF with N / N after pasting on machine cylinder
The primary charging potential is Vd^Two, Primary charging when transfer current is ON
Potential Vd^ThreeAs | Vd ^Two-Vd^Three| Was measured.

Further, as a measurement of a photo memory with respect to white light, an electrophotographic photosensitive member newly produced by the same method as described above was attached to a cylinder of a modified machine similar to the above, and the initial dark area potential (N / N) was determined. Vd) / initial light portion potential (V
The charging and image exposure light amounts are set so that 1) becomes -700 (V) /-200 (V), and then the electrophotographic photoreceptor is masked so that a dark portion and a bright portion are formed. After irradiating light at 3000 lux for 20 minutes, the sample was left for 5 minutes, and the potential was measured in the same manner, and the absolute value (ΔVd ⁴ ) of the change from the initial value of the dark portion potential was measured as a photo memory. The results are shown in Table 18 below.

[Examples 35] to [67] Examples except that the pigment and / or the charge transporting material of Example 34 were changed as shown in Tables 18 to 19 below as the charge generating material. An electrophotographic photoreceptor was prepared in the same manner as in No. 34, and the same evaluation was performed. Table 18 shows the results.
To Table 19 below.

[0152]

[Table 18]

[0153]

[Table 19]

[Comparative Examples 35] to [Comparative Example 68] [0154] Except that the pigment and / or the charge transporting material of Example 34 were changed as shown in Tables 20 to 21 below as the charge generating substance, An electrophotographic photoreceptor was prepared in the same manner as in No. 34, and the same evaluation was performed. Table 20 shows the results.
To Table 21.

[0155]

[Table 20]

[0156]

[Table 21]

The structure of the comparative charge transporting material is as follows (H
-17) The compounds shown in [Formula 17] to (H-24) [Formula 24] were used.

[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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As is clear from the results of Tables 18 to 21, the chlorogallium phthalocyanine compound and the hydroxygallium phthalocyanine compound as the charge generating materials indicated by the present invention and the general formula (3) as the charge transporting material.
The electrophotographic photoreceptor in which the charge transport compound having a specific structure represented by is combined, has high sensitivity, low residual potential,
Potential fluctuations in various environments are extremely small and have stable characteristics. Further, it is clear that transfer memory, photo memory, and the like also exhibit extremely small and excellent characteristics.

Example 68 An undercoat layer similar to that of Example 34 was formed on an aluminum sheet substrate having a thickness of 50 μm by bar coating, and a charge transport layer similar to that of Example 34 was further formed thereon by a thickness of 18 μm. Formed.

Next, 6 parts of bisphenol Z type polycarbonate was dissolved in 66 parts of cyclohexanone, and 4.0 parts of hydroxygallium phthalocyanine of pigment No. P-4 shown in Table 11 was mixed with the solution, and dispersed in a sand mill for 20 hours. After that, bisphenol Z-type polycarbonate 5
And 9 parts of the charge transport material used in Example 34 were dissolved,
Further, 40 parts of tetrahydrofuran and 40 parts of dichloromethane were added and diluted to obtain a dispersion paint.

This paint was applied onto the charge transport layer by a spray coating method and dried to form a charge generation layer having a thickness of 5 μm, thereby producing an electrophotographic photosensitive member (working photosensitive member No. 68).

Example 69 A chlorogallium phthalocyanine having a crystal form of pigment number P-1 shown in Table 11 was used in place of pigment number P-4 of Example 68 as a charge generating substance. An electrophotographic photosensitive member (working photosensitive member No. 69) was produced in the same manner as in Example 68.

[Comparative Example 69] [0171] Comparative Example 69 was carried out except that Comparative Pigment Number Q-1 (τ-type metal-free phthalocyanine) shown in Table 12 was used instead of Pigment Number P-4 of Example 68 as the charge generating substance. An electrophotographic photosensitive member (comparative photosensitive member No. 69) was produced in the same manner as in Example 68.

[Comparative Example 70] [0172] The same procedure as in Example 68 was performed except that Comparative Pigment No. Q-2 (ε-type copper phthalocyanine) shown in Table 12 was used instead of Pigment No. P-4 of Example 68 as the charge generating substance. An electrophotographic photoreceptor (comparative photoreceptor No. 70) was produced in the same manner as in Example 68.

[Comparative Example 71] A comparative pigment number Q-3 (β-type oxytitanium phthalocyanine) shown in Table 12 was used in place of the pigment number P-4 of Example 68 as a charge generating substance. An electrophotographic photoreceptor (comparative photoreceptor No. 71) was produced in the same manner as in Example 68.

[Comparative Example 72] Instead of pigment number P-4 of Example 68 as a charge generating substance, comparative pigment number Q-4 (black angle 2θ ± 0.2 ° in X-ray diffraction of CuKα) shown in Table 12 was used. An electrophotographic photoreceptor (Comparative Photoreceptor No. 72) was produced in the same manner as in Example 68 except that oxytitanium phthalocyanine having peaks at 9.6 ° and 27.2 ° was used.

The thus obtained electrophotographic photosensitive members of Examples 68 and 69 and Comparative Examples 69 to 72 were subjected to an electrostatic tester (EP
A-8100: manufactured by Kawaguchi Electric Co., Ltd.).

In the evaluation, first, the surface potential was set to +700 (V) by positive corona charging, and then the surface potential was lowered to +200 (V) by exposure to monochromatic light of 802 nm which was separated by a monochromator. The amount of light at that time was measured and used as sensitivity. The results are shown in Table 22.

[0177]

[Table 22]

Example 70 An N-methoxymethylated 6 nylon resin (weight average molecular weight 4500) was formed on an aluminum substrate.
0) 4.2 parts and 8.8 parts of alcohol-soluble copolymerized nylon resin (weight average molecular weight: 50,000)
A solution dissolved in 0 part was applied with a Meyer bar, and an undercoat layer having a thickness of 0.5 μm after drying was provided.

As the charge generating material, 12 parts of pigment number P-4 hydroxygallium phthalocyanine shown in Table 11, 10 parts of polyvinyl butyral resin (butyralization ratio: 65%, weight average molecular weight: 45,000) and 200 parts of cyclohexanone
Was dispersed with a ball mill disperser for 14 hours. This dispersion was applied on the undercoat layer prepared previously by a blade coating method to prepare a charge generation layer having a thickness of 0.25 μm after drying.

Next, the above-mentioned exemplified compound no. 104 to 5.
No. 0 and No. 107 of 5.0 parts of polyarylate resin (weight-average molecular weight: 50,000) and 70 parts of monochlorobenzene are dissolved in 70 parts of monoarylbenzene, coated on the previously prepared charge generating layer by a blade coating method, and dried. Fifteen
A μm charge transport layer was prepared.

The photoreceptor produced in this manner was supplied with -5 kV
Was subjected to corona discharge. At this time, the surface potential (initial potential V0) was measured. Further, the surface potential of this photoreceptor when left in a dark place for 1 second was measured. The sensitivity is the exposure amount (E) required to attenuate the potential (V1) after dark decay to 1/5.
_1/5 : μJ / cm ² ). At this time, a quaternary semiconductor laser of indium / gallium / aluminum / phosphorus (output: 5 mW;
An oscillation wavelength of 680 nm) was used. The results were as follows.

V0: -700 (V) V1: -695 (V) E _1/5 : 0.30 (μJ / cm ² ) Next, a reversal developing type electrophotographic printer equipped with a semiconductor laser as described above. The photoreceptor was mounted on a laser beam printer (LBP-SX manufactured by Canon Inc.), and an actual image forming test was performed. The conditions are as follows.

Surface potential for primary charging: -700 (V) Surface potential for image exposure: -150 (V) Transfer potential: +700 volts Development polarity: negative polarity Process speed: 50 (mm / sec) Development condition (development bias) : -450 (V) Image exposure scan method: Image scan Exposure before primary charging: 50 (lux / sec) full red exposure Image formation was performed by line scanning laser beam according to character signals and image signals. Good prints were obtained for both images.

Further, when 5000 images were continuously output, stable prints were obtained from the initial stage to 5000 sheets.

[0185]

As described in the present invention, by using a gallium phthalocyanine compound, particularly preferably a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound, as a charge generating material in combination with a compound having a specific structure as a charge transporting material, It has high sensitivity in the long wavelength region such as the oscillation wavelength of a laser diode, shows excellent potential characteristics stably regardless of repeated use or environmental fluctuations, and gives good image quality without image defects such as fog. Further, it is possible to provide an electrophotographic photosensitive member having an extremely small transfer memory and photo memory, and a process cartridge and an electrophotographic apparatus using the same.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of chlorogallium phthalocyanine obtained in Production Example 1 (KBr tablet method)

FIG. 2 is a powder X-ray diffraction diagram of chlorogallium phthalocyanine obtained in Production Example 1.

FIG. 3 shows a Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 2 of 7.4 °, 16.6 °,
X-ray diffraction pattern of chlorogallium phthalocyanine having crystal forms with strong peaks at 25.5 ° and 28.2 °

FIG. 4 shows a Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 3 of 8.7 ° to 9.2 °, 1
X-ray diffraction pattern of chlorogallium phthalocyanine having crystal forms with strong peaks at 7.5 °, 24.0 °, 27.4 ° and 28.7 °

FIG. 5 is an infrared absorption spectrum of the hydroxygallium phthalocyanine obtained in Production Example 4 (KBr tablet method).

6 is an X-ray of hydroxygallium phthalocyanine having a crystal form having strong peaks at Bragg angles 2θ ± 0.2 ° of 6.8 ° and 26.2 ° in X-ray diffraction of CuKα obtained in Production Example 4. FIG. Diffractogram

FIG. 7 is an X-ray of hydroxygallium phthalocyanine having a crystal form having strong peaks at Bragg angles 2θ ± 0.2 ° of 7.4 ° and 28.2 ° in X-ray diffraction of CuKα obtained in Production Example 5. Diffractogram

FIG. 8 shows a Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα obtained in Production Example 6 of 7.5 °, 16.3 °,
X-ray diffraction pattern of hydroxygallium phthalocyanine having crystal forms with strong peaks at 24.9 ° and 26.4 °

9 shows a Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα obtained in Production Example 7 of 6.9 °, 13.3 °,
X-ray diffraction pattern of hydroxygallium phthalocyanine having crystal forms with strong peaks at 16.5 ° and 26.7 °

FIG. 10 is a schematic cross-sectional view of a layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 11 is a schematic cross-sectional view of a layer structure of the electrophotographic photosensitive member of the present invention.

FIG. 12 is a view showing a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photoreceptor 2 axis 3 primary charging means 4 exposure light 5 developing means 6 transfer means 7 transfer material 8 image fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge

Claims (24)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains at least one kind selected from a gallium phthalocyanine compound as a charge generating substance, and as a charge transporting substance. The following general formula (1) [Formula 1] [Wherein, Ar ¹ represents an aryl group which may have a substituent; R ¹ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. R ² represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent;
However, Ar ¹ is represented by the following general formula (2): (Wherein, R ³ and R ⁴ each represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom;
R ³ and R ⁴ may be the same or different; Ar
² represents an aryl group which may have a substituent; n represents 0 or an integer of 1 to 2; ) Has at least one substituent; R ¹ and R ² or R ¹ and Ar ¹ or Ar ² and R
⁴ may form a ring directly or via another organic residue. An electrophotographic photoreceptor comprising at least one compound represented by the formula: 2. The electrophotographic photosensitive member according to claim 1, wherein the gallium phthalocyanine compound is at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound. 3. The electrophotographic photosensitive member according to claim 1, wherein R ^{4 in the} general formula (2) is an aryl group which may have a substituent. 4. The compound represented by the general formula (1), wherein R ¹ in the formula is an aryl group which may have a substituent. The electrophotographic photosensitive member according to the above. 5. The electrophotographic photosensitive member according to claim 1, wherein n in the general formula (2) is 0. 6. The chlorogallium phthalocyanine compound has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2% is 7.4%, 16.6%, 25.5%, and 2
The electrophotographic photoreceptor according to any one of claims 2 to 5, wherein the photoreceptor is a crystal type having a strong peak at 8.2 °. 7. The chlorogallium phthalocyanine compound has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ゜ is 8.7 ゜ -9.2 ゜, 17.5 ゜, 24.0
The electrophotographic photoreceptor according to any one of claims 2 to 5, wherein the photoreceptor is of a crystal type having strong peaks at {, 27.4} and 28.7}. 8. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle 2θ in X-ray diffraction of CuKα.
The electrophotographic photoreceptor according to any one of claims 2 to 5, wherein ± 0.2 ° is a crystal type having strong peaks at 6.8 ° and 26.2 °. 9. The method according to claim 8, wherein the hydroxygallium phthalocyanine compound has a Bragg angle 2θ in X-ray diffraction of CuKα.
The electrophotographic photosensitive member according to any one of claims 2 to 5, wherein ± 0.2 ° is a crystal type having strong peaks at 7.4 ° and 28.2 °. 10. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle of 2 in X-ray diffraction of CuKα.
The crystal form having a strong peak at θ ± 0.2 ° at 7.5 °, 16.3 °, 24.9 ° and 26.4 °. Electrophotographic photoreceptor. 11. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle of 2 in X-ray diffraction of CuKα.
The crystal form having a strong peak at θ ± 0.2 ° at 6.9 °, 13.3 °, 16.5 °, and 26.7 °. Electrophotographic photoreceptor. 12. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains at least one kind selected from a gallium phthalocyanine compound as a charge generating substance, and as a charge transporting substance. The following general formula (3): (Wherein, Ar ₃ and Ar ₄ each represent an arylene group which may have a substituent; R ₅ , R ₇ and R ₈ each represent an alkyl group which may have a substituent, R ₆ represents an optionally substituted aralkyl group or an optionally substituted aryl group; R ₆ represents an optionally substituted alkyl group or an optionally substituted aralkyl group; Or 1; R ₅ and R ₆ or R ₅ and Ar ₃ or A
r ₄ and R ₇ or Ar ₃ and Ar ₄ may form a ring directly or via another organic residue. An electrophotographic photoreceptor comprising at least one compound represented by the formula: 13. The electrophotographic photoreceptor according to claim 12, wherein the gallium phthalocyanine compound is at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound. 14. When n = 0 in the general formula (3), R
14. The electrophotographic photosensitive member according to claim 12, wherein ₅ is an aryl group which may have a substituent. 15. When n = 1 in the general formula (3), R
14. The electrophotographic photosensitive member according to claim 12, wherein ₅ and R ₇ are each an aryl group which may have a substituent. 16. When n = 0 in the general formula (3), A
r ₃ is a phenylene group which may have a substituent; Ar ₄ is a phenyl group which may have a substituent; when n = 1, Ar ₃
16. The electrophotographic photoconductor according to claim 12, wherein Ar ₄ and Ar ₄ are each a phenylene group which may have a substituent. 17. The method according to claim 17, wherein the chlorogallium phthalocyanine compound has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.4 °, 16.6 °, 25.5 °, and 2
17. The electrophotographic photoreceptor according to claim 13, wherein the photoreceptor is a crystal type having a strong peak at 8.2 [deg.]. 18. The chlorogallium phthalocyanine compound may have a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 8.7 ° to 9.2 °, 17.5 °, 24.0
The electrophotographic photoreceptor according to any one of claims 13 to 16, wherein the electrophotographic photoreceptor is a crystal type having strong peaks at 0 °, 27.4 ° and 28.7 °. 19. The method according to claim 19, wherein the hydroxygallium phthalocyanine compound has a Bragg angle of 2 in X-ray diffraction of CuKα.
The crystal form having θ ± 0.2 ° having strong peaks at 6.8 ° and 26.2 °.
The electrophotographic photosensitive member according to any one of the above. 20. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle of 2 in X-ray diffraction of CuKα.
17. A crystal form in which θ ± 0.2 ° has strong peaks at 7.4 ° and 28.2 °.
The electrophotographic photosensitive member according to any one of the above. 21. The hydroxygallium phthalocyanine compound has a Bragg angle of 2 in X-ray diffraction of CuKα.
The crystal form having strong peaks at θ ± 0.2 ° of 7.5 °, 16.3 °, 24.9 ° and 26.4 °, 17. Electrophotographic photoreceptor. 22. The hydroxygallium phthalocyanine compound has a Bragg angle of 2 in X-ray diffraction of CuKα.
The crystal form having strong peaks at θ ± 0.2 ° of 6.9 °, 13.3 °, 16.5 °, and 26.7 °. Electrophotographic photoreceptor. 23. An electrophotographic apparatus, wherein the electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit are integrally supported. A process cartridge which is detachably mounted on a process cartridge. 24. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a cleaning unit.