JP5168822B2 - Electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, image forming apparatus, and phthalocyanine crystal - Google Patents

Description

  The present invention relates to a phthalocyanine crystal obtained by converting a crystal form of a phthalocyanine crystal precursor, an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge, and an image forming apparatus using the phthalocyanine crystal. In particular, phthalocyanine that has high sensitivity to LED light and semiconductor laser light, and has little fluctuation in sensitivity to humidity changes in the usage environment, and can be suitably used as a material for solar cells, electronic paper, electrophotographic photoreceptors, etc. The present invention relates to a crystal, and an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge, and an image forming apparatus using the phthalocyanine crystal.

  In recent years, organic optical devices that use organic photoconductive materials and can be used for solar cells, electronic paper, electrophotography, and the like have been intensively studied. Among these, in particular, the electrophotographic technique is excellent in immediacy and can obtain a high-quality image. Therefore, in recent years, it has been widely applied not only to the field of copying machines but also to various printers and printing machines.

  As a photoreceptor that is the core of electrophotographic technology, a photoreceptor using an inorganic photoconductive material such as selenium, an arsenic-selenium alloy, and zinc oxide has been used, but recently, it is pollution-free. Photoconductors using organic photoconductive materials, which have advantages such as easy film formation / manufacturing and high freedom of material selection / combination, are the mainstream.

  The sensitivity of an electrophotographic photoreceptor using an organic photoconductive material varies depending on the wavelength of exposure light and the type of charge generating material.

  As a charge generation material having sensitivity to light having a long wavelength of 600 to 800 nm, phthalocyanine compounds have been attracting attention. Researches on metal-containing phthalocyanines such as magnesium phthalocyanine and oxytitanium phthalocyanine, or metal-free phthalocyanines have been conducted energetically.

  Regarding phthalocyanine compounds, it has been reported that even if the monomolecular structure is the same, the charge generation efficiency differs depending on the arrangement order (crystal type) of crystals that are aggregates of single molecules (non-patent literature). 1 and 2).

  In recent years, with the speeding up and full color of the electrophotographic process in copying machines, laser printers, plain paper fax machines, etc., the characteristics of the electrophotographic photosensitive member are required to have high sensitivity and high speed response. There is a need to develop charge generation materials with higher sensitivity.

  For high sensitivity, a charge generation material having a high charge generation capability is required. Among them, active research has been conducted on oxytitanium phthalocyanine, which is highly sensitive to LD exposure, which is currently the mainstream. The oxytitanium phthalocyanine is known to exhibit crystal polymorphism. Known crystal types include α-type (see Patent Literature 1), β-type (see Patent Literature 2), C-type (see Patent Literature 3), D-type (see Patent Literature 4), and Y-type (see Patent Literature 5). ), M type (refer to Patent Document 6), M-α type (refer to Patent Document 7), I type (refer to Patent Document 8), etc., have been reported.

  Among these crystal types, a crystal type having a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-ray (wavelength 1.541Å) (hereinafter sometimes referred to as “specific crystal type” as appropriate). Are known to exhibit high quantum efficiency and high sensitivity.

  In addition to crystals composed only of oxytitanium phthalocyanine molecules alone, mixed crystals composed of oxytitanium phthalocyanine and other phthalocyanines and other pigments form the above specific crystal type and exhibit high sensitivity. Is widely known (see Patent Document 9).

  However, the phthalocyanine crystal exhibiting the specific crystal form described above is obtained by performing a conversion of the crystal form of the obtained phthalocyanine crystal precursor after passing through a method for producing a phthalocyanine crystal precursor, which is usually called the acid pasting method. Therefore, the influence of the acid used in the acid pasting method remains even after the crystal form is converted, and there is a problem that the charging property is deteriorated.

  The problem of this deterioration in chargeability is that a charger is used to charge the surface of the photoconductor to a uniform potential when an electrophotographic photoconductor is produced using a phthalocyanine crystal as a material and is used in a laser printer, a copying machine or the like. It appears as an issue of increasing power consumption. In particular, tandem type electrophotographic apparatuses, which have become the mainstream in full-color laser printers and copying machines that have become widespread in recent years, use a plurality of photoconductors, and a charger for each of the plurality of photoconductors. Therefore, when an electrophotographic photosensitive member with poor charging property is used, the increase in the number of chargers causes a significant increase in power consumption of the charger. For this reason, it becomes a big barrier and a problem in reducing the power consumption of the entire electrophotographic apparatus.

  In order to solve the problem of deterioration of the charging property, a phthalocyanine crystal precursor is produced using a mechanical grinding method without using the acid pasting method, and the crystal form of the obtained phthalocyanine crystal precursor is converted. Thus, a method for producing a phthalocyanine crystal exhibiting the above-mentioned specific crystal type (see Patent Document 10) has been studied. However, in this method using mechanical grinding, a uniform phthalocyanine crystal precursor is obtained. However, it has many problems in terms of productivity and manufacturing stability. For this reason, a method for producing a phthalocyanine crystal having the above-mentioned specific crystal type has been widely desired as a method for producing a phthalocyanine crystal with improved chargeability and stable and high productivity, but it has not been developed yet. It is.

Journal of Electrophotographic Society, Vol. 29, No. 3, pp. 250-258 Journal of Electrophotographic Society, Vol. 32, No. 3, pp. 282-289 JP-A-61-217050 JP-A 62-67094 JP-A-63-366 JP-A-2-8265 JP 63-20365 A JP-A-3-54265 JP-A-3-54264 Japanese Patent Laid-Open No. 3-128973 Japanese Patent Laid-Open No. 3-9962 Japanese Patent Laid-Open No. 3-9962

  The phthalocyanine crystal having the specific crystal type is produced by bringing a phthalocyanine as a precursor into contact with a specific compound and converting the crystal type. In this crystal type conversion step, the crystal type is constructed by the interaction between the molecule of the compound to be contacted and the phthalocyanines. At this time, the interaction with the phthalocyanines differs depending on the compound used, and various crystals are produced depending on the production method. Shows type and particle shape. In addition, characteristics of the electrophotographic photosensitive member such as charge generation capability (sensitivity), chargeability, and dark decay depend on the manufacturing method, and it is very difficult to predict the performance in advance.

  As described above, the phthalocyanine crystal having the specific crystal type has high sensitivity, but has a problem that the characteristics greatly change due to changes in the environment in which it is used. As described above, since it is very difficult to predict the crystal form and characteristics of the phthalocyanine crystal obtained by the production method, the phthalocyanine crystal having the above-mentioned specific crystal form is more sensitive, and Despite the widespread demand for phthalocyanine crystals with good chargeability, the present situation is that they have not been developed yet.

  The present invention has been made in view of the above demand. That is, an object of the present invention is to provide a phthalocyanine crystal having high sensitivity and excellent chargeability, and by using this phthalocyanine crystal, an electron having high sensitivity and chargeability is also provided. An electrophotographic photosensitive member cartridge that can provide a photographic photosensitive member, and that can stably provide an image having a high image quality, has excellent charging properties, and can reduce power consumption by using the electrophotographic photosensitive member. And providing an image forming apparatus.

  The present inventors presume that the compound used for converting the crystal form of the phthalocyanine crystal precursor is deeply involved in the sensitivity fluctuation with respect to the change in humidity of the obtained electrophotographic photosensitive member, and solves the above problems. As a result of diligent investigations, a phthalocyanine crystal precursor was formed into an organic compound (non-amino organic compound) having no unsubstituted or substituted amino group in the presence of a compound (amino compound) having an unsubstituted or substituted amino group. The phthalocyanine crystal obtained by bringing the crystal into contact with each other has high sensitivity and is excellent in chargeability. Also, by using this phthalocyanine crystal, it has high sensitivity and is charged. The present inventors have found that an electrophotographic photoreceptor excellent in performance can be obtained, and have completed the present invention.

That is, the gist of the present invention is that, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, the photosensitive layer contains a phthalocyanine crystal, and the phthalocyanine crystal is a primary amine compound or a secondary amine. CuKα characteristic X is obtained through a process of converting the crystal form by bringing amorphous phthalocyanines or low crystalline phthalocyanines into contact with an organic compound having no unsubstituted or substituted amino group in the presence of an amine compound. It has a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to a line (wavelength 1.541 mm), and has no distinct peak at 26.2 ° or 28.6 °. The present invention resides in an electrophotographic photosensitive member.

Another subject matter of the present invention is an electrophotographic photosensitive member comprising the above-described electrophotographic photosensitive member and a cartridge case that detachably supports the electrophotographic photosensitive member with respect to an image forming apparatus. It exists in a body cartridge (Claim 2 ).

Another gist of the present invention is the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, and an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image. , characterized by comprising a developing unit for developing an electrostatic latent image formed on the electrophotographic photosensitive member, it lies in the image forming apparatus (claim 3).
Furthermore, another gist of the present invention is to provide an amorphous phthalocyanine or a low crystalline phthalocyanine in an organic compound having no unsubstituted or substituted amino group in the presence of a primary amine compound or a secondary amine compound. Is obtained through a step of converting the crystal form by bringing into contact with each other, and shows a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-ray (wavelength 1.541Å); It exists in the phthalocyanine crystal | crystallization characterized by not having a clear peak at 2 degrees or 28.6 degrees (Claim 4 ) .

The phthalocyanine crystal of the present invention has an advantage that it has high sensitivity and is excellent in chargeability.
In addition, the electrophotographic photosensitive member of the present invention has an advantage that it has high sensitivity and excellent chargeability.
In addition, the electrophotographic photosensitive member cartridge and the image forming apparatus of the present invention have the advantages of being able to stably provide an image with high image quality, being excellent in chargeability and reducing power consumption.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.

[I. Phthalocyanine crystal]
[Composition of phthalocyanine crystals]
In the present invention, “phthalocyanine crystal” refers to a crystal containing one or more phthalocyanine compounds. That is, not only a crystal composed of only one kind of phthalocyanine compound, but also a mixed crystal composed of a plurality of kinds of phthalocyanine compounds and a mixed crystal composed of one or more kinds of phthalocyanine compounds and other molecules. In the invention, it is referred to as “phthalocyanine crystal”.

  In the present invention, the “phthalocyanine compound” refers to a compound having a phthalocyanine skeleton. Specific examples include metal-free phthalocyanines; phthalocyanines having a planar molecular structure such as copper phthalocyanine, zinc phthalocyanine, lead phthalocyanine; oxytitanium phthalocyanine, oxyvanadium phthalocyanine, chloroaluminum phthalocyanine, chlorogallium phthalocyanine, chloroindium phthalocyanine, hydroxygallium Examples thereof include phthalocyanines whose molecules have a shuttlecock structure; phthalocyanines whose molecules have a top structure such as dichlorotin phthalocyanine, dichlorosilicon phthalocyanine, dihydroxytin phthalocyanine and dihydroxysilicon phthalocyanine.

  When the phthalocyanine crystal of the present invention is composed of a single type of phthalocyanine compound, a phthalocyanine compound having a shuttlecock structure is desirable in view of the characteristics as an electrophotographic photoreceptor. Further, among the phthalocyanine compounds having a shuttlecock structure, since the characteristics as an electrophotographic photoreceptor are generally good, the central metal of the phthalocyanine compound molecule is in the form of an oxide, chloride, or hydroxide. From the viewpoint of ease of production of phthalocyanine crystals, it is more preferable that the central metal take the form of an oxide. As a specific example, oxytitanium phthalocyanine or oxyvanadium phthalocyanine is particularly preferable, and oxytitanium phthalocyanine is most preferable.

  On the other hand, as a case where the phthalocyanine crystal of the present invention is a mixed crystal composed of a plurality of types of molecules, as described above, it is composed of a plurality of types of phthalocyanine compounds (that is, does not include compounds other than phthalocyanine compounds). , One or two or more phthalocyanine compounds and a compound other than one or two or more phthalocyanine compounds (that is, including compounds other than phthalocyanine compounds). From the above, it is preferred to be composed of a plurality of types of phthalocyanine compounds (that is, not containing compounds other than phthalocyanine compounds).

  When the phthalocyanine crystal of the present invention is a mixed crystal, it is preferable to contain a phthalocyanine compound having a shuttlecock structure as a main component in consideration of the characteristics as an electrophotographic photosensitive member. The phthalocyanine compound contained as the main component (hereinafter referred to as “main component phthalocyanine compound” as appropriate) is preferably such that the central metal of the molecule is in the form of an oxide, chloride or hydroxide. From the viewpoint of ease of production, it is more preferable that the central metal is in the form of an oxide. As a specific example, oxytitanium phthalocyanine or oxyvanadium phthalocyanine is particularly preferable, and oxytitanium phthalocyanine is most preferable. The content of the main component phthalocyanine compound is usually 60% by weight or more with respect to the mixed crystal phthalocyanine crystal, but if the amount contained is small, the crystal form controllability is lowered, so 70% by weight or more. It is preferably 80% by weight or more from the viewpoint of crystal stability during dispersion, and more preferably 85% by weight or more from the viewpoint of characteristics when used as an electrophotographic photoreceptor.

  Further, when the phthalocyanine crystal of the present invention is a mixed crystal, the phthalocyanine compound contained in addition to the above-mentioned main component phthalocyanine compound (hereinafter referred to as “phthalocyanine compound other than main component” as appropriate) is stable crystal as a mixed crystal. From the viewpoint of properties, a phthalocyanine compound having a shuttlecock structure or a phthalocyanine compound having a planar molecular structure is preferable. Among these, from the viewpoint of electrophotographic photoreceptor characteristics, among phthalocyanine compounds having a shuttlecock structure, oxyvanadium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, and chloroindium phthalocyanine are preferable, and among phthalocyanine compounds having a planar structure, Metal-free phthalocyanine, zinc phthalocyanine, and lead phthalocyanine are preferred. Among these, oxyvanadium phthalocyanine, chlorogallium phthalocyanine, chloroindium phthalocyanine, hydroxygallium phthalocyanine, and metal-free phthalocyanine are more preferable, and since there are more vacant spaces in the mixed crystal, metal-free phthalocyanine having a planar molecular structure. Is particularly preferred. Only one type of phthalocyanine compound other than the main component may be used, or two or more types may be used in any combination and ratio, but it is preferable to use only one type. The content of the phthalocyanine compound other than the main component is usually 40% by weight or less with respect to the phthalocyanine crystal which is a mixed crystal, but if it is too much, the crystal form controllability is lowered, so 30% by weight or less is preferable. 20% by weight or less is preferable from the viewpoint of stability during dispersion, and 15% by weight or less is preferable from the viewpoint of electrophotographic characteristics. However, if the content of the phthalocyanine compound other than the main component is too small, the effect of the content cannot be obtained. Therefore, the content is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more.

[Phthalocyanine crystal precursor]
The phthalocyanine crystal of the present invention is obtained through a step of converting a crystal form by bringing a phthalocyanine crystal precursor into contact with a non-amino organic compound described later in the presence of an amino compound described later. Here, the “phthalocyanine crystal precursor” refers to a substance from which a phthalocyanine crystal can be obtained by performing a treatment for converting a crystal form (hereinafter sometimes referred to as “crystal form conversion treatment”). Therefore, the phthalocyanine crystal precursor may be any of a kind of phthalocyanine compound, a mixture of two or more phthalocyanine compounds, a mixture of one or two or more phthalocyanine compounds and one or two or more other compounds. (In the following description, a phthalocyanine compound or a mixture containing a phthalocyanine compound may be collectively referred to as “phthalocyanines”). In addition, although the existence state is not particularly limited, in consideration of the controllability of the crystal type at the time of crystal conversion, the phthalocyanine crystal precursor is usually preferably an amorphous phthalocyanine or a low crystalline phthalocyanine.

  In the present invention, “low crystalline phthalocyanines” means a Bragg to CuKα characteristic X-ray (wavelength 1.541Å) in a powder X-ray diffraction (X-ray diffraction: hereinafter sometimes abbreviated as “XRD”) spectrum. An angle (2θ ± 0.2 °) refers to phthalocyanines having no peak with a half-value width of 0.30 ° or less within a range of 0 ° to 40 °. If this half-value width is too small, the phthalocyanine molecule will have a certain degree of regularity and long-term order in the solid, and the crystal form controllability will be reduced when the crystal form is converted. From the above, the low crystalline phthalocyanines used as phthalocyanine crystal precursors in the present invention have a half-value width of usually 0.35 ° or less, more preferably 0.40 ° or less, and particularly 0.45 ° or less. It is preferable that

  In the present specification, measurement of powder X-ray diffraction spectrum of phthalocyanines, determination of Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray (wavelength 1.541 波長), and calculation of peak half-value width are as follows: It shall be performed under the following conditions.

As an apparatus for measuring a powder X-ray diffraction spectrum, a concentrated optical system powder X-ray diffractometer (for example, PW1700 manufactured by PANalytical) using CuKα (CuKα ₁ + CuKα ₂ ) rays as an X-ray source is used.

  The measurement conditions of the powder X-ray diffraction spectrum are as follows: scanning range (2θ) 3.0 to 40.0 °, scanning step width 0.05 °, scanning speed 3.0 ° / min, divergence slit 1 °, scattering slit 1 °. The light receiving slit is 0.2 mm.

The peak half width can be calculated by a profile fitting method. Profile fitting can be performed using, for example, powder X-ray diffraction pattern analysis software JADE5.0 + manufactured by MDI. The calculation conditions are as follows. That is, the background is fixed at an ideal position from the entire measurement range (2θ = 3.0 to 40.0 °). As the fitting function, a Peason-VII function considering the contribution of CuKα ₂ is used. Three variables of the fitting function are refined: diffraction angle (2θ), peak height, and peak half-value width (β _o ). The influence of CuKα ₂ is removed, and the diffraction angle (2θ), peak height, and peak half width (β _o ) derived from CuKα ₁ are calculated. The asymmetry is fixed at 0 and the shape constant is fixed at 1.5.

The peak half-value width (β _o ) calculated by the above profile fitting is the peak half width (2θ = 28.442 °) of the standard Si (NIST Si 640b) calculated by the same measurement conditions and the same profile fitting conditions. By correcting according to the following equation by β _Si ), the half width (β) derived from the sample is obtained.

  The boundary between the low crystalline phthalocyanines and the amorphous phthalocyanines is not clear, but any of them can be used as a preferred phthalocyanine crystal precursor in the present invention. In the following description, when the low crystalline phthalocyanines and the amorphous phthalocyanines are referred to without particular distinction, they are collectively referred to as “low crystalline / amorphous phthalocyanines”.

  As will be described later, as the crystal form of the phthalocyanine crystal of the present invention, a crystal form having a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-ray (wavelength 1.541Å) ( Specific crystal type) is preferable, but low crystalline phthalocyanines having a peak near 27.2 ° have regularity somewhat similar to the phthalocyanine crystal having the specific crystal type. Excellent crystal form controllability. In this case, the low crystalline phthalocyanine has a half-value width that usually does not have a peak of 0.30 ° or less, preferably does not have a peak of 0.35 ° or less, and more preferably The half width does not have a peak of 0.40 ° or less, and particularly preferably the half width does not have a peak of 0.45 ° or less.

  On the other hand, when low crystalline / amorphous phthalocyanines having no peak near 27.2 ° are used as the phthalocyanine crystal precursor, the crystal form controllability to the phthalocyanine crystal having the specific crystal type is low. It is desirable that the crystallinity is low. The low crystalline phthalocyanine in this case is one that does not have a peak whose half width is usually 0.30 ° or less, preferably one that does not have a peak whose half width is 0.50 ° or less, More preferably, the half width does not have a peak of 0.70 ° or less, and further preferably the half width does not have a peak of 0.90 ° or less.

  2 to 5 show examples of powder X-ray diffraction spectra of low crystalline / amorphous phthalocyanines. These X-ray diffraction spectra are illustrated for the purpose of explaining the present invention in detail, and phthalocyanines that can be used as phthalocyanine crystal precursors in the present invention are used unless they violate the scope of the present invention. However, the present invention is not limited to the low crystalline / amorphous phthalocyanines having these X-ray diffraction spectra.

  Crystalline phthalocyanines (phthalocyanine crystals) are usually in a state where phthalocyanine molecules have a certain regularity or long-term order in a solid, and have a clear peak when measured by a powder X-ray diffraction spectrum . On the other hand, low crystalline / amorphous phthalocyanines are in a state in which the regularity of the molecular arrangement and the long-term order of the molecular arrangement are lowered in the solid, and the powder X-ray diffraction spectrum illustrated as FIGS. Thus, even if it shows a halo figure or has a peak, its full width at half maximum is very wide.

  In the present invention, the low crystalline / amorphous phthalocyanines to be used as phthalocyanine crystal precursors are known as chemical treatment methods such as acid paste method and acid slurry method, and mechanical treatment methods such as grinding and grinding. However, since a more uniform low crystalline / amorphous phthalocyanine can be obtained, the chemical treatment method is preferable, and the acid paste method is more preferable.

[Amino compound]
In the phthalocyanine crystal of the present invention, the above-mentioned phthalocyanine crystal precursor is brought into contact with a non-amino organic compound described later in the presence of a compound having an unsubstituted or substituted amino group (this is appropriately abbreviated as “amino compound”). And obtained by converting the crystal form.

  In the present invention, the term “unsubstituted or substituted amino group” refers to an unsubstituted amino group, a monosubstituted amino group, and a disubstituted amino group. Here, the “unsubstituted amino group”, “monosubstituted amino group”, and “disubstituted amino group” are each a functional group represented by a portion surrounded by a broken line in the following formulas (i) to (iii). It shall be said.

・ Unsubstituted amino group:

-Monosubstituted amino group:

・ Disubstituted amino group:

  Since the amino compound used in the present invention exhibits the above-mentioned effect by having the above-mentioned unsubstituted or substituted amino group in the structure, at least one unsubstituted or substituted amino group per molecule is present. As long as it has, there is no particular limitation on the number. However, when the number of unsubstituted or substituted amino groups is too large, the solubility in water becomes higher than the solubility in non-amino organic compounds described later, and the obtained effect tends to be reduced. Therefore, the number of unsubstituted or substituted amino groups per molecule of amino compound is preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less. In addition, when an amino compound has two or more unsubstituted or substituted amino groups per molecule, these unsubstituted or substituted amino groups may be the same as or different from each other.

  The amino compound used in the present invention has a primary amine compound, a secondary amine compound, and a tertiary amine, depending on which of an unsubstituted amino group, a mono-substituted amino group, and a di-substituted amino group, respectively. Classified as amine compounds. Specifically, the primary amine compound, the secondary amine compound, and the tertiary amine compound are compounds having structures represented by the following general formulas (I) to (III), respectively.

・ Primary amine compounds:

・ Secondary amine compounds:

Tertiary amine compound:

In the amino compound used in the present invention, the organic residue moiety attached to the nitrogen atom to form an unsubstituted or substituted amino group [A ¹ in the general formula (I), A ² in the general formula (II) And the structure of A ³ and A ^{4 to} A ⁶ in the general formula (III) is not particularly limited. A molecule of a phthalocyanine compound (hereinafter sometimes abbreviated as “phthalocyanine molecule”) has a large number of π electrons in the structure. Since phthalocyanine molecules are constructed by the interaction of developed π electrons with each other, the larger the interaction between the phthalocyanine molecule and the amino compound, the more the amino compound in the phthalocyanine crystal Easy to import. Therefore, it is preferable that the organic residue portion of the amino compound has a structure having π electrons so that the interaction between the amino compound and the phthalocyanine molecule is strengthened. The number of π electrons that the organic residue part of the amino compound has is not particularly limited as long as it contains at least two π electrons (that is, at least one carbon-carbon double bond) per molecule of the amino compound. . However, the organic residue portion preferably includes a structure having aromaticity that satisfies the Hückel rule. The structure having aromaticity may be any structure as long as the structure satisfies the Hückel rule, but if the structure of the aromatic ring portion is too large, harmful effects such as a decrease in solubility increase. In the formula 4n + 2 (n is an integer), n is preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less.

  Examples of structures having aromaticity include aromatic rings consisting of hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, perylene, pyrrole, thiophene, furan, silole, pyridine, indole, benzothiophene, benzofuran, Aromatic rings containing heteroatoms such as quinoline, isoquinoline, phenanthrene and the like can be mentioned. Especially, from the surface of the solubility with respect to the below-mentioned non-amino organic compound, the number of the elements which comprise the aromatic ring in the organic residue part of an amino compound becomes like this. Preferably it is 14 or less, More preferably, it is 10 or less. Specifically, an aromatic ring made of hydrocarbon is more preferable, and benzene is particularly preferable.

Examples of specific structures of the organic residue portions A ^{1 to} A ⁶ that the amino compound used in the present invention has include an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an acyl group, a thiocarbonyl group, A hydroxy group, a sulfo group, etc. are mentioned. Of these, alkyl, aryl, aralkyl, halogenated alkyl, acyl, and sulfo are preferred from the viewpoint of versatility and safety of the reagent, and alkyl, aryl, and aralkyl are more preferred.

The molecular weight of the organic residue parts A ^{1 to} A ⁶ possessed by the amino compound used in the present invention is not particularly limited, but if the molecular volume of these organic residue parts A ^{1 to} A ⁶ is too large, it will enter the phthalocyanine crystal. These organic residue moieties A ^{1 to} A ⁶ usually have a molecular weight of 500 or less, preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less.

In addition, two organic residue parts [A ² and A ³ in the general formula (II)] possessed by the secondary amine compound and three organic residue parts [the general formula (III Any two or three of A ^{4 to} A ⁶ ] in the above) may be directly bonded to each other or may have a cyclic structure by bonding via a bridging atom or a divalent organic residue. Is possible.

  The amino compound used in the present invention is preferably a primary amine compound or a secondary amine compound from the viewpoint of the effect obtained when incorporated in the phthalocyanine crystal. Among primary amine compounds and secondary amine compounds, from the viewpoint of versatility and stability of reagents, usually monoalkylamine, monoarylamine, monoaralkylamine, monoacylamine, hydrazone, dialkylamine, diarylamine , Diaralkylamine, alkylarylamine, alkylaralkylamine, arylaralkylamine, diacylamine, imide, lactam, hydroxylamine and the like are used. In particular, considering the characteristics of the electrophotographic photosensitive member using the obtained phthalocyanine crystal as a material, monoalkylamine, monoarylamine, monoaralkylamine, dialkylamine, diarylamine, diaralkylamine, alkylarylamine, alkylaralkyl Amine, arylaralkylamine, monoacylamine, diacylamine, imide, and lactam are preferable, and monoarylamine, diarylamine, diaralkylamine, alkylarylamine, alkylaralkylamine, and arylaralkylamine are more preferable.

  Examples of the structure of the amino compound preferably used in the present invention are given below. However, the following structures are merely shown as examples, and the structures of amino compounds that can be used in the present invention are not limited to the following examples, and may be any structures as long as they do not contradict the spirit of the present invention. Amino compounds can be used. In the structural formulas below, “Me” represents a methyl group, and “Ac” represents an acetyl group.

  As the state of the amino compound, a state in which the amino compound is intact, a state in which the amino compound is ionized, a state in which the ionized amino compound is bonded to a counter ion to form a salt, and the like are conceivable. In the present invention, since the amino compound itself is efficiently incorporated into the phthalocyanine crystal, it can be assumed that the unsubstituted or substituted amino group moiety contributes to the expression of the effect. Therefore, the amino compound is in any of the above states. There may be. However, in consideration of the influence of the obtained phthalocyanine crystal on the characteristics of the electrophotographic photoreceptor, it is preferable to use the amino compound as it is.

  In addition, the presence form of the amino compound is not particularly limited, and may be any of liquid, gas, and solid.

  In addition, as an amino compound, any 1 type may be used independently and 2 or more types may be used together by arbitrary combinations and a ratio.

[Non-amino organic compounds]
In the phthalocyanine crystal of the present invention, the above phthalocyanine crystal precursor is an organic compound having no unsubstituted or substituted amino group in the presence of the above amino compound (this is abbreviated as “non-amino organic compound” as appropriate). ).

  The non-amino organic compound used in the present invention is an unsubstituted or substituted amino group (that is, an unsubstituted amino group, a mono-substituted amino group, a di-substituted amino group) described in the above [Amino compound] column. Is an organic compound that does not exist in the structure. The type of the non-amino organic compound used in the present invention is not particularly limited as long as it has an ability to convert a crystal form.

  Non-amino organic compounds can be roughly classified into aliphatic compounds and aromatic compounds (in the following description, these are appropriately referred to as “non-amino aliphatic compounds” and “non-amino aromatic compounds”, respectively). To do.)

  Examples of non-amino aliphatic compounds include saturated or unsaturated aliphatic hydrocarbon compounds such as pinene, terpyrenone, hexane, cyclohexane, octane, decane, 2-methylpentane, ligroin, petroleum benzine; diethyl ether, diisopropyl ether, Aliphatic ether compounds such as dibutyl ether, dimethyl cellosolve, ethylene glycol dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,2 Halogenated aliphatic compounds such as 1,2-tetrachloroethane; aliphatic ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone; Aliphatic ester compounds such as methyl, propyl acetate, butyl acetate, isobutyl acetate, hexyl acetate, butyl acrylate, methyl propionate, cyclohexyl acetate; aliphatic alcohol compounds such as methanol, ethanol, butanol; normal propyl aldehyde, normal butyraldehyde And the like, and the like. The hydrocarbon skeleton possessed by these non-amino aliphatic compounds may be a chain (which may be linear or branched) or cyclic, and is a combination of linear and cyclic. There may be.

  On the other hand, examples of non-amino aromatic compounds include aromatic hydrocarbon compounds such as toluene, xylene, naphthalene, biphenyl, and terphenyl; monochlorobenzene, dichlorobenzene, trichlorobenzene, dichlorotoluene, 1-chloronaphthalene, bromobenzene, and the like. Halogenated aromatic compounds: aromatic nitro compounds such as nitrobenzene and 2-fluoronitrobenzene, aromatic ester compounds such as methyl benzoate, butyl benzoate, methyl 2-chlorobenzoate, methyl 2-methylbenzoate and phenylacetate Aromatic ether compounds such as diphenyl ether, anisole and chloroanisole; aromatic aldehyde compounds such as benzaldehyde and 2-chlorobenzaldehyde; aromatic ketone compounds such as acetophenone and 2-chloroacetophenone; Thiophene, furan, quinoline, and the like heterocyclic aromatic compounds picoline.

  Among these non-amino organic compounds, an aliphatic compound, an aromatic compound or an aromatic hydrocarbon compound containing a halogen atom or an oxygen atom is preferable from the viewpoint of crystal form conversion ability. Among these, in consideration of the stability during dispersion of the obtained phthalocyanine crystal, a halogenated aliphatic compound, an aliphatic ether compound, an aliphatic ketone compound, an aliphatic ester compound, an aromatic hydrocarbon compound, a halogenated aromatic compound, Aromatic nitro compounds, aromatic ketone compounds, aromatic ester compounds, and aromatic aldehyde compounds are more preferable. From the viewpoint of the characteristics of electrophotographic photoreceptors using the obtained phthalocyanine crystals as materials, aliphatic ether compounds, halogenated compounds Aromatic compounds, aromatic nitro compounds, aromatic ketone compounds, aromatic ester compounds, and aromatic aldehyde compounds are more preferred.

  These non-amino organic compounds may belong to a plurality of compound groups at the same time among the above-described compound groups depending on the types of substituents in the structure (for example, nitrochlorobenzene is a “halogenated aromatic compound”). And the “aromatic nitro compound”), the non-amino organic compound is judged to have the attributes of the compound as having all the attributes of the plurality of classifications ( For example, nitrochlorobenzene has the attributes of both halogenated aromatics and aromatic nitro compounds).

  Further, the non-amino organic compound has a functional group showing acidity in its structure (hereinafter, abbreviated as “acidic functional group” as appropriate) from the viewpoint of controllability of the crystal type when brought into contact with the phthalocyanine crystal. Preferably not. An acidic functional group is a functional group that functions to show the acidity that an organic acid has in the structure. Examples include a carboxyl group, a thiocarboxyl group, a dithiocarboxyl group, a mercaptocarbonyl group, a hydroperoxy group, and a sulfo group. , Sulfino group, sulfenoic acid group, phenolic hydroxyl group, thiol group, phosphinico group, phosphono group, selenono group, selenino group, seleneno group, arsinico group, arsono group, boronic acid group, boranoic acid group and the like.

  The molecular weight of the non-amino organic compound is not particularly limited, but the contact treatment between the non-amino organic compound and the phthalocyanine crystal precursor is usually performed in a liquid state. Too large is not desirable. Specifically, the molecular weight of the non-amino organic compound is usually 1000 or less, preferably 500 or less, more preferably 400 or less, and still more preferably 300 or less. On the other hand, if the molecular weight of the non-amino organic compound is too small, the boiling point is generally low, and since it tends to volatilize, the handleability during production tends to decrease, so the lower limit of the molecular weight is usually 50 or more, preferably 100 or more. It is.

  The presence form of the non-amino organic compound is not particularly limited and may be any of liquid, gas, and solid, but the contact treatment between the non-amino organic compound and the phthalocyanine crystal precursor is usually performed when the non-amino organic compound is liquid. Since it is performed in a state, the melting point of the non-amino organic compound is usually 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.

  Any one of these non-amino organic compounds may be used alone, or two or more thereof may be used in any combination and ratio.

[Combination of amino compound and non-amino organic compound]
It is unclear why the combined use of amino compounds and non-amino organic compounds during the crystal conversion treatment of phthalocyanine crystal precursors affects the characteristics of electrophotographic photoreceptors using the resulting phthalocyanine crystals as materials. However, it is presumed that the effect of the present invention is obtained by the coexistence of the non-amino organic compound during the crystal conversion treatment, whereby the amino compound used at the same time is more efficiently taken into the phthalocyanine crystal.

[Contact procedure]
The method for bringing the non-amino organic compound into contact with the phthalocyanine crystal precursor in the presence of the amino compound is not particularly limited, and any known method can be used.

  Among them, it is common to contact a phthalocyanine crystal precursor with a non-amino organic compound in the presence of water and an amino compound, which is suitable for obtaining the phthalocyanine crystal of the present invention. When water is used, the amount used is not particularly limited, but the weight ratio to the amino compound is usually 100% by weight or more, particularly 500% by weight or more, and usually 5000% by weight or less, especially 1500% by weight or less. It is preferable to do.

  As a specific contact method between the non-amino organic compound and the phthalocyanine crystal precursor in the presence of the amino compound, for example, the phthalocyanine crystal precursor is converted into a vapor or liquid containing the non-amino organic compound and the amino compound, or non-amino. A method in which a solution containing an organic compound and an amino compound is allowed to coexist with stirring, and a phthalocyanine crystal precursor and a non-amino organic compound in the presence of an amino compound are mixed in an automatic mortar, planetary mill, vibrating ball mill, CF mill, roller Examples thereof include a method in which physical force is applied together with media in an apparatus such as a mill, a sand mill, or a kneader.

  The temperature at the time of contact between the non-amino organic compound and the phthalocyanine crystal precursor in the presence of the amino compound is not particularly limited, but is usually 150 ° C. or lower. Therefore, it is desirable that both the non-amino organic compound and amino compound used in the present invention have a melting point of usually 150 ° C. or lower. If the melting points of the non-amino organic compound and the amino compound are too high, the handling properties of the non-amino organic compound and the amino compound at the time of crystal conversion are lowered. Therefore, the melting point is preferably 120 ° C. or less, more preferably 80 It is below ℃.

  The phthalocyanine crystal of the present invention is obtained by contact treatment with a non-amino organic compound in the presence of an amino compound (that is, crystal form conversion treatment). The obtained phthalocyanine crystal of the present invention may be washed with water, various organic solvents, or the like as necessary. The phthalocyanine crystal of the present invention obtained after the contact treatment or after washing is usually in a wet cake state. As described above, the effect of the present invention is obtained by bringing an amino compound into a phthalocyanine crystal when the phthalocyanine crystal precursor is brought into contact with a non-amino organic compound in the presence of the amino compound at the time of crystal conversion. Therefore, the content of the phthalocyanine in the wet cake of the phthalocyanine crystal of the present invention after the contact treatment or after washing (the weight of the phthalocyanine relative to the total weight of the wet cake) is not particularly limited, and any amount There may be.

  The wet cake of phthalocyanine crystals of the present invention obtained after the contact treatment or after washing is usually subjected to a drying step. The drying method can be dried by a known method such as blow drying, heat drying, vacuum drying or freeze drying.

  The phthalocyanine crystal of the present invention obtained by the above method usually takes a form in which primary particles aggregate to form secondary particles. The particle size varies greatly depending on the conditions and formulation when contacting the non-amino organic compound in the presence of an amino compound, but considering the dispersibility, the primary particle size is preferably 500 nm or less, and the coating film formability In view of the above, it is preferably 250 nm or less.

  In the present invention, the definition of whether or not crystal transformation was performed before and after the contact between the phthalocyanine crystal precursor and the non-amino organic compound in the presence of the amino compound is as follows. That is, when each peak of the powder X-ray diffraction spectrum is completely the same before and after the contact, it is defined that the crystal is not converted, and the peak position obtained from the powder X-ray diffraction spectrum before and after the contact, the presence / absence of the peak, If there is any difference in information such as price range, it is defined that the crystal has been transformed.

[Crystal form of phthalocyanine crystal]
The crystal form of the phthalocyanine crystal of the present invention may be any crystal form as long as it is different from that of the phthalocyanine crystal precursor, and in particular, an electrophotography when the phthalocyanine crystal is used as a material for an electrophotographic photosensitive member. From the viewpoint of the characteristics of the photoreceptor, a crystal type having a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-rays (wavelength 1.541Å) (in this specification, this crystal type Is preferably referred to as “specific crystal form”).

  Although the mechanism by which the effect of the present invention is obtained is not clear, when the phthalocyanine crystal precursor is brought into contact with a non-amino organic compound to construct the crystal type, the amino compound coexists so that the amino compound becomes a phthalocyanine crystal. Incorporated into the phthalocyanine crystal, the unsubstituted or substituted amino group of the incorporated amino compound interacts with impurities deteriorating the charging property, thereby reducing the charging property. It may be because it is preventing.

  In particular, the above-mentioned specific crystal type has a lower crystal density than other crystal types, and there are many vacant spaces in the crystal. Therefore, a non-amino organic compound is used as a phthalocyanine crystal precursor in the presence of an amino compound. When the above-mentioned specific crystal type is constructed by bringing them into contact, it is considered that the amino compound is easily taken into the phthalocyanine crystal and plays a role of preventing deterioration of the charging property in the phthalocyanine crystal. For the above reasons, the phthalocyanine crystal of the present invention preferably has the above-mentioned specific crystal type.

When the phthalocyanine crystal of the present invention has the above-mentioned specific crystal type, the following (i) to (iii) are exemplified as a combination of clear peaks shown together with the peak at 27.2 °.
(I) 9.6 °, 24.1 °, 27.2 °
(Ii) 9.5 °, 9.7 °, 24.1 °, 27.2 °
(Iii) 9.0 °, 14.2 °, 23.9 °, 27.1 °

  Among them, among the combinations of the peaks (i) to (iii), those showing the combination of the peaks (i) or (ii) are preferable because of excellent crystal stability during dispersion.

  In particular, crystal forms having main diffraction peaks at 7.3 °, 9.6 °, 11.6 °, 14.2 °, 18.0 °, 24.1 ° and 27.2 °, or 7.3 A crystal type having main diffraction peaks at °, 9.5 °, 9.7 °, 11.6 °, 14.2 °, 18.0 °, 24.2 ° and 27.2 ° is an electrophotographic photoreceptor. From the standpoint of dark decay and residual potential when used as a material.

  Note that a phthalocyanine crystal having a peak near 26.2 ° or 28.6 ° rearranges to another crystal type at the time of dispersion, and causes a reduction in electrophotographic characteristics. Therefore, the phthalocyanine crystal of the present invention has 26.2 °. It is preferable that there is no clear peak around ° or 28.6 °.

  As described above, the effect of the non-amino organic compound and the amino compound in the phthalocyanine crystal of the present invention is that when the phthalocyanine crystal precursor and the non-amino organic compound are brought into contact with each other in the presence of the amino compound during crystal conversion, It is considered that the compound is obtained by being incorporated into a phthalocyanine crystal and does not depend on the orientation of molecules in the crystal. Therefore, in the preferred peak combinations listed above, the intensity ratio between the peaks is considered to have no correlation with the effect of the present invention. Therefore, these peaks may have any intensity ratio, but usually the peak near 27.2 ° or the peak near 9.6 ° is often the largest.

[Chlorinated oxytitanium phthalocyanine]
In the case of an oxytitanium phthalocyanine crystal (a crystal or mixed crystal containing at least oxytitanium phthalocyanine) suitable as the phthalocyanine crystal of the present invention, oxytitanium phthalocyanine (chlorinated) in which the phthalocyanine ring is chlorinated due to the difference in the production method Oxytitanium phthalocyanine) may be contained. Since the effect of the present invention is considered to be manifested by the inclusion of an amino compound in the phthalocyanine crystal, there is a lot of space in the oxytitanium phthalocyanine crystal so that a large amount of the amino compound is incorporated. Is preferred. Chlorinated oxytitanium phthalocyanine has a chloro group in the phthalocyanine ring portion, and its molecular volume is larger than that of unsubstituted oxytitanium phthalocyanine. For this reason, when chlorinated oxytitanium phthalocyanine is present in the crystal, the space for taking in the amino compound is reduced. For the above reasons, oxytitanium phthalocyanines (hereinafter referred to as “oxytitanium phthalocyanine crystal precursors”) used as phthalocyanine crystal precursors for the production of oxytitanium phthalocyanine crystals have a chlorinated oxytitanium phthalocyanine content. Less is preferable.

  The content of chlorinated oxytitanium phthalocyanine in the oxytitanium phthalocyanine crystal precursor can be determined by a conventionally known elemental analysis method and mass spectrum measurement. Among them, various methods described in the column of <Mass Spectrum Measurement Method> of JP-A-2001-115054 can be used as the method of mass spectrum measurement. Specific conditions for elemental analysis and mass spectrum measurement include the following conditions, for example.

<Chlorine content measurement conditions (elemental analysis)>
About 100 mg of oxytitanium phthalocyanine crystal precursor is precisely weighed and placed on a quartz board, and completely combusted in a temperature rising type electric furnace (for example, QF-02 manufactured by Mitsubishi Chemical Corporation), and the combustion gas is 15 ml of water. Absorb quantitatively. The obtained absorbing solution is diluted to 50 ml and subjected to chlorine analysis by ion chromatography (“DX-120” manufactured by Dionex). The ion chromatography conditions are shown below.

Column: Dionex IonPak AG12A + AS12A
Eluent: 2.7 mM sodium carbonate (Na ₂ CO ₃ ) /0.3 mM sodium bicarbonate (NaHCO ₃ )
Flow rate: 1.3ml / min
Injection volume: 50 μl

<Mass spectrum measurement conditions>
(A) Sample preparation:
0.50 g of oxytitanium phthalocyanine crystal precursor is placed in a 50 ml glass container together with 30 g of glass beads (φ1.0 to 1.4 mm) and 10 g of cyclohexanone, and dispersed for 3 hours with a dye dispersion tester (paint shaker). A 5% by weight oxytitanium phthalocyanine dispersion is obtained. 1 μl of this 5 wt% oxytitanium phthalocyanine dispersion is collected in a 20 ml sample bottle, 5 ml of chloroform is added, and the mixture is dispersed by ultrasonic waves for 1 hour to prepare a 10 ppm oxytitanium phthalocyanine dispersion.

(B) Measuring equipment and conditions:
Measuring device: JMS-700 / MStaion made by JEOL
Ionization mode: DCI (-)
Reaction gas: isobutane (ionization chamber pressure 1 × 10 ⁻⁵ Torr)
Filament rate: 0-> 0.90A (1A / min)
Mass spectrometry: 2000
Scanning method: MF-Linear
Scan mass range: 500 to 600
Total mass range scan time: 0.8 sec
Repeat time: 0.5 sec

(C) Calculation method of mass spectral peak intensity ratio between chlorinated oxytitanium phthalocyanine and unsubstituted oxytitanium phthalocyanine:
1 μl of 10 ppm oxytitanium phthalocyanine dispersion prepared in the above procedure is applied to the filament of the DCI probe, and mass spectrum measurement is performed under the above conditions. In the obtained mass spectrum, peak areas obtained from ion chromatography of m / z = 610 corresponding to the molecular ion of chlorinated oxytitanium phthalocyanine and m / z = 576 corresponding to the molecular ion of unsubstituted oxytitanium phthalocyanine. The ratio (“610” peak area / “576” peak area) is calculated as the mass spectrum peak intensity ratio.

  The amount of chlorinated oxytitanium phthalocyanine contained in the oxytitanium phthalocyanine crystal precursor obtained by measurement based on the above <chlorine content measurement conditions (elemental analysis)> is preferably 0.4% by weight or less. Preferably it is 0.3 weight% or less, More preferably, it is 0.2 weight% or less.

  Moreover, the mass spectrum peak intensity ratio between chlorinated oxytitanium phthalocyanine and unsubstituted oxytitanium phthalocyanine in the oxytitanium phthalocyanine crystal precursor obtained by measurement based on the above <mass spectrum measurement conditions> is preferably 0.050. Hereinafter, it is more preferably 0.040 or less, and still more preferably 0.030 or less.

[II. Electrophotographic photoreceptor]
Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail. The electrophotographic photosensitive member of the present invention has a photosensitive layer on a conductive support, and the photosensitive layer contains the phthalocyanine crystal of the present invention described above.

[II-1. Conductive support]
As the conductive support, for example, a metal material such as aluminum, aluminum alloy, stainless steel, copper, nickel, or a resin material imparted with conductivity by adding conductive powder such as metal, carbon, tin oxide, Mainly used are resin, glass, paper, or the like obtained by depositing or coating a conductive material such as aluminum, nickel, ITO (indium tin oxide) on the surface. As the shape, a drum shape, a sheet shape, a belt shape or the like is used. Alternatively, a conductive support made of a metal material may be used in which a conductive material having an appropriate resistance value is applied for the purpose of controlling conductivity, surface properties, etc., or for covering defects.

  The surface of the conductive support may be smooth, or may be roughened by using a special cutting method or polishing. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. In order to reduce the cost, it is possible to use the drawing tube as it is without cutting. In particular, when using a non-cutting aluminum substrate such as drawing, impact processing, ironing, etc., it is preferable because the treatment eliminates dirt, foreign matter, and other foreign matters, small scratches, etc., and a uniform and clean substrate can be obtained. .

Moreover, when using metal materials, such as an aluminum alloy, as an electroconductive support body, you may use, after giving an anodic oxide film. Anodized film is formed, for example, by anodizing in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, boric acid, sulfamic acid, etc. give. In the case of anodic oxidation in sulfuric acid, the sulfuric acid concentration is 100 to 300 g / l, the dissolved aluminum concentration is 2 to 15 g / l, the liquid temperature is 15 to 30 ° C., the electrolysis voltage is 10 to 20 V, and the current density is 0.5 to Although it is preferable to set within the range of ² A / dm ² , it is not limited to the above conditions.

  If the average film thickness of the anodized film is too thick, strong sealing conditions may be required due to high concentration of the sealing liquid, high temperature / long-time treatment, and the like. Accordingly, the productivity tends to deteriorate, and surface defects such as spots, dirt, and dusting tend to occur on the coating surface. From such a point, it is preferable that the average film thickness of the anodic oxide coating is usually 20 μm or less, particularly 7 μm or less.

  When an anodized film is formed, it is preferable to perform a sealing treatment. The sealing treatment may be performed by a normal method, for example, a low-temperature sealing treatment in which the sealing material is immersed in an aqueous solution containing nickel fluoride as a main component, or a high-temperature sealing in which the sealing treatment is immersed in an aqueous solution containing nickel acetate as a main component. It is preferable to apply a hole treatment.

  In the case of low-temperature sealing treatment, the concentration of the nickel fluoride aqueous solution to be used can be selected as appropriate, but more preferable results are obtained when the concentration is in the range of 3 to 6 g / l. The pH of the aqueous nickel fluoride solution is usually 4.5 or higher, preferably 5.5 or higher, and usually 6.5 or lower, preferably 6.0 or lower. As the pH adjuster, oxalic acid, boric acid, formic acid, acetic acid, sodium hydroxide, sodium acetate, aqueous ammonia and the like can be used. In order to further improve the physical properties of the film, cobalt fluoride, cobalt acetate, nickel sulfate, a surfactant, and the like may be included in the nickel fluoride aqueous solution. The treatment temperature is usually in the range of 25 ° C. or higher, preferably 30 ° C. or higher, and usually 40 ° C. or lower, preferably 35 ° C. or lower, in order to facilitate the sealing treatment. The treatment time is preferably in the range of 1 to 3 minutes per 1 μm of film thickness. Subsequently, it is washed with water and dried to finish the low temperature sealing treatment.

  In the case of high-temperature sealing treatment, as the sealing agent, an aqueous metal salt solution such as nickel acetate, cobalt acetate, lead acetate, nickel acetate-cobalt, and barium nitrate can be used, and nickel acetate is particularly preferable. When using nickel acetate aqueous solution, it is preferable to use the density | concentration within the range of 5-20 g / l normally. It is preferable to treat the nickel acetate aqueous solution usually at a pH in the range of 5.0 to 6.0. As the pH regulator, aqueous ammonia, sodium acetate, or the like can be used. In order to improve the physical properties of the film, sodium acetate, an organic carboxylic acid, an anionic or nonionic surfactant may be contained in the nickel acetate aqueous solution. The treatment temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and usually 100 ° C. or lower, preferably 98 ° C. or lower. The treatment time is usually 10 minutes or longer, preferably 20 minutes or longer. Subsequently, it is washed with water and dried to finish the high temperature sealing treatment.

[II-2. Undercoat layer]
An undercoat layer may be provided between the conductive support and the photosensitive layer described later for improving adhesion and blocking properties. As the undercoat layer, a binder resin, a binder resin in which particles such as metal oxide are dispersed, and the like are used.

  Examples of the metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium titanate and barium titanate. Any one of these metal oxide particles may be used alone, or a plurality of these metal oxide particles may be mixed and used in an arbitrary combination and ratio. Among these metal particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Moreover, the thing of a several crystal state may contain.

  Various particle sizes can be used as the particle size of the metal oxide particles. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle size is usually 10 nm or more, usually 100 nm or less, particularly 50 nm or less. Those are preferred.

  The undercoat layer is preferably formed in a form in which the metal oxide particles are dispersed in a binder resin. As binder resin used for the undercoat layer, epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, Polyimide resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacrylic acid resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyvinyl pyridine resin, water-soluble polyester resin, nitro Cellulose ester resins such as cellulose, cellulose ether resins, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelate Compounds, organic zirconium compounds such as zirconium alkoxide compounds, titanyl chelate compounds, organic titanyl compounds such as titanyl alkoxide compound, may be a known binder resin such as a silane coupling agent. These can be used alone or in a cured form together with a curing agent. Among these, alcohol-soluble copolymerized polyamide, modified polyamide, and the like are preferable because they exhibit good dispersibility and coatability.

  The use ratio of the metal oxide particles with respect to the binder resin can be arbitrarily selected, but from the viewpoint of the stability of the dispersion and the coating property, it is usually used in the range of 10% by weight to 500% by weight. preferable.

  In addition, the undercoat layer may contain pigment particles, resin particles, and the like for the purpose of preventing image defects.

  The thickness of the undercoat layer can be arbitrarily selected, but it is usually 0.01 μm or more, particularly 0.1 μm or more, and usually 30 μm or less, especially 20 μm or less from the viewpoint of photoreceptor characteristics and applicability. Is preferred.

[II-3. Photosensitive layer]
A photosensitive layer is formed on the conductive support (on the undercoat layer when an undercoat layer is provided). The photosensitive layer includes a charge generation material, a charge transport material, and a binder resin.

  As the structure of the photosensitive layer, a charge generation material and a charge transport material are dispersed in a binder resin and exist in the same layer (hereinafter referred to as “single layer type photosensitive layer” as appropriate), and charge generation. A photosensitive layer having a laminated structure in which a substance is dispersed into a charge generation layer in which a substance is dispersed in a binder resin and a charge transport layer in which a charge transport substance is dispersed in a binder resin (hereinafter, referred to as “laminated photosensitive layer” as appropriate). Any of these can be used. In the case of a laminated type photosensitive layer, a layered photosensitive layer is laminated in the order of a charge generation layer and a charge transport layer from the conductive support side, and a charge transport layer and a charge generation layer are laminated in this order from the side of the conductive support. Although it is divided into a reverse lamination type photosensitive layer, any of them can be applied. Hereinafter, each structure will be described.

<Charge generation layer of laminated photosensitive layer>
The charge generation layer of the multilayer photosensitive layer is prepared by dissolving or dispersing a binder resin in a solvent or dispersion medium and dispersing a charge generation material to prepare a coating solution. By coating and forming a film on the body (on the undercoat layer when an undercoat layer is provided) or on the charge transport layer in the case of a reverse laminated type photoreceptor, and binding fine particles of the charge generating material with a binder resin It is formed.

・ Charge generating materials:
As the charge generating substance, at least the phthalocyanine crystal of the present invention is used. Any one kind of the phthalocyanine crystals of the present invention may be used alone, but two or more kinds may be used in any combination and ratio. Further, only the phthalocyanine crystal of the present invention may be used as a charge generation material, but the phthalocyanine crystal of the present invention may be combined with other charge generation materials and used in a mixed state.

  The particle size of the phthalocyanine crystal of the present invention used as a charge generation material needs to be sufficiently small. Specifically, it is preferably 1 μm or less, more preferably 0.5 μm or less.

  Examples of other charge generation materials used in a mixed state with the phthalocyanine crystal of the present invention include various known dyes and pigments. Examples of dyes include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium pigment), quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, benzimidazole pigments, and the like. . Of these, phthalocyanine pigments and azo pigments are preferably used from the viewpoint of photosensitivity.

・ Binder resin:
The type of the binder resin in the charge generation layer is not particularly limited. Examples thereof include polyvinyl butyral resin, polyvinyl formal resin, polyvinyl such as partially acetalized polyvinyl butyral resin in which a part of butyral is modified with formal or acetal. Acetal resin, polyarylate resin, polycarbonate resin, polyester resin, modified ether polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, polyacrylamide resin , Polyamide resin, polyvinyl pyridine resin, cellulosic resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, casein, salt Vinyl chloride-vinyl acetate copolymer such as vinyl-vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Copolymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin, silicone-alkyd resin, phenol-formaldehyde resin and other insulating resins, poly-N-vinylcarbazole, polyvinylanthracene, It can be selected from organic photoconductive polymers such as polyvinyl perylene, but is not limited to these polymers. In addition, any one of these binder resins may be used alone, or two or more of these binder resins may be mixed and used in an arbitrary combination and ratio.

・ Combination ratio:
The compounding ratio (weight) of the binder resin and the charge generation material in the charge generation layer is usually 10 parts by weight or more, preferably 30 parts by weight or more, and usually 1000 parts by weight, based on the ratio of the charge generation material to 100 parts by weight of the binder resin. The range is not more than parts by weight, preferably not more than 500 parts by weight. If the ratio of the charge generation material is too high, the stability of the coating solution tends to decrease due to problems such as aggregation of the charge generation material, while if too low, the sensitivity as a photoreceptor tends to decrease. Therefore, it is preferable to use within the above range.

・ Solvent or dispersion medium:
Examples of the solvent or dispersion medium used for preparing the coating liquid include saturated aliphatic solvents such as pentane, hexane, octane, and nonane; aromatic solvents such as toluene, xylene, and anisole; chlorobenzene, dichlorobenzene, and chloronaphthalene. Halogenated aromatic solvents such as amide solvents such as dimethylformamide and N-methyl-2-pyrrolidone; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and benzyl alcohol; fats such as glycerin and polyethylene glycol Aliphatic polyhydric alcohols; chain and cyclic ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, 4-methoxy-4-methyl-2-pentanone; ester solvents such as methyl formate, ethyl acetate, n-butyl acetate; Methylene, chloroform Halogenated hydrocarbon solvents such as 1,2-dichloroethane; chain and cyclic ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve; acetonitrile, dimethyl sulfoxide , Sulfolane, aprotic polar solvents such as hexamethyl phosphate triamide; nitrogen-containing compounds such as n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine; mineral oil such as ligroin; And those which do not dissolve the undercoat layer described above are preferably used. Any one of these solvents or dispersion media may be used alone, or two or more thereof may be used in any combination and ratio.

・ Distribution method:
As a method of dispersing the charge generation material in a solvent or a dispersion medium, a known dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. At this time, it is effective to refine the charge generating material particles to a particle size of usually 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

・ Film thickness:
The film thickness of the charge generation layer is usually 0.1 μm or more, preferably 0.15 μm or more, usually 10 μm or less, preferably 0.6 μm or less.

<Charge transport layer of laminated photosensitive layer>
The charge transport layer of the multilayer photosensitive layer is prepared by dissolving or dispersing the binder resin in a solvent and dispersing the charge transport material to prepare a coating solution. In the case of a multilayer type photoreceptor, it is formed by coating on a conductive support (or on the undercoat layer when an undercoat layer is provided) and binding fine particles of a charge transport material with a binder resin.

・ Binder resin:
Examples of the binder resin include polymers and copolymers of vinyl compounds such as butadiene resin, styrene resin, vinyl acetate resin, vinyl chloride resin, acrylic ester resin, methacrylic ester resin, vinyl alcohol resin, ethyl vinyl ether, and polyvinyl butyral. Resin, polyvinyl formal resin, partially modified polyvinyl acetal, polycarbonate resin, polyester resin, polyarylate resin, polyamide resin, polyurethane resin, cellulose ester resin, phenoxy resin, silicone resin, silicone-alkyd resin, poly-N-vinylcarbazole resin, etc. Is mentioned. These binder resins may be modified with a silicon reagent or the like. Of the binder resins, polycarbonate resins and polyarylate resins are particularly preferable.

  Among polycarbonate resins and polyarylate resins, polycarbonate resins and polyarylate resins containing a bisphenol residue and / or a biphenol residue represented by the following structural formula are preferable from the viewpoint of sensitivity and residual potential. To polycarbonate resin is more preferable. In addition, a plurality of structural formulas enclosed in parentheses indicate that they have partial structures represented by the respective structural formulas, and there are no particular restrictions on the order in which these partial structures are combined. And

These binder resins can also be used after being crosslinked with heat, light or the like using an appropriate curing agent.
In addition, any one kind of binder resin may be used alone, or two or more kinds may be mixed and used in an arbitrary combination and ratio.

・ Charge transport materials:
The charge transport material is not particularly limited as long as it is a known material. For example, aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, diphenoquinone, etc. Electron withdrawing substances such as quinone compounds, carbazole derivatives, indole derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, heterocyclic compounds such as benzofuran derivatives, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, Examples thereof include butadiene derivatives, enamine derivatives and those obtained by bonding a plurality of these compounds, or electron donating substances such as polymers having groups composed of these compounds in the main chain or side chain. Among these, carbazole derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable.

・ Combination ratio:
The ratio of the binder resin to the charge transport material is usually 20 parts by weight or more with respect to 100 parts by weight of the binder resin, and preferably 30 parts by weight or more from the viewpoint of reducing the residual potential. From the viewpoint, 40 parts by weight or less is more preferable. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, it is usually 150 parts by weight or less, preferably 120 parts by weight or less from the viewpoint of compatibility between the charge transport material and the binder resin, and 100 from the viewpoint of printing durability. The amount is preferably not more than parts by weight, and particularly preferably not more than 80 parts by weight from the viewpoint of scratch resistance.

-Solvent or dispersion medium and dispersion method:
The type of the solvent or dispersion medium and the method for dispersing the charge transport material in the solvent or dispersion medium are as described in the section <Charge generation layer of laminated photosensitive layer>.

・ Film thickness:
The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, particularly 10 μm or more, and usually 50 μm or less, especially 45 μm or less, and further 30 μm or less from the viewpoints of long life, image stability, and high resolution. It is preferable to set it as the range.

<Single layer type photosensitive layer>
A single-layer type photosensitive layer is obtained by applying a coating solution obtained by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin on a conductive support (on the undercoat layer when an undercoat layer is provided). And the fine particles of the charge generation material and the charge transport material are bound by a binder resin. As the charge generation material, those described in the section <Charge generation layer of multilayer photosensitive layer> are used. As the charge transport material and the binder resin, those of <Charge transport layer of multilayer photosensitive layer> are used. Those described in the column are used. The ratios of the charge generation material and the charge transport material to the binder resin are also as described in the above sections <Charge generation layer of multilayer photosensitive layer> and <Charge transport layer of multilayer photosensitive layer>, respectively.

  If the phthalocyanine crystal dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity tends not to be obtained, and if it is too much, there is a tendency for the charging property and the sensitivity to deteriorate. For example, the ratio of the charge generating material to 100 parts by weight of the binder resin is preferably in the range of 0.1% by weight or more, more preferably 1% by weight or more, and preferably 50% by weight or less, more preferably 20% by weight or less. Used in.

The kind of the solvent or dispersion medium and the dispersion method are as described in the above section <Charge generation layer of laminated photosensitive layer>.
The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.

<Other ingredients>
The photosensitive layer has well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds to improve film-forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. In addition, additives such as a leveling agent and a visible light shielding agent may be contained.

[II-4. Other layers]
As the configuration of the electrophotographic photosensitive member, in addition to the above-described layers, other layers may be provided without departing from the spirit of the present invention.

For example, a protective layer may be provided on the photosensitive layer for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to a discharge substance generated from a charger or the like. The protective layer is formed by containing a conductive material in an appropriate binder resin, or charge transport such as a triphenylamine skeleton as described in JP-A-9-190004, JP-A-10-252377, etc. A copolymer using a compound having a function can be used. Examples of the conductive material include aromatic amino compounds such as TPD (N, N′-diphenyl-N, N′-bis- (m-tolyl) benzidine), antimony oxide, indium oxide, tin oxide, titanium oxide, and tin oxide. -Metal oxides such as antimony oxide, aluminum oxide, and zinc oxide can be used, but are not limited thereto. As the binder resin used for the protective layer, known resins such as polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, and siloxane resin can be used. Also, a copolymer of the above resin and a skeleton having a charge transporting ability such as a triphenylamine skeleton as described in JP-A-9-190004 and JP-A-10-252377 can be used. The protective layer is preferably configured to have an electric resistance of 10 ⁹ to 10 ¹⁴ Ω · cm. If the electrical resistance is too high, the residual potential tends to increase and an image with a lot of fog tends to be formed. On the other hand, if the electrical resistance is too low, the image tends to be blurred and the resolution is lowered. In addition, the protective layer must be configured so as not to substantially impede transmission of light irradiated for image exposure.

  The surface layer (photosensitive layer) of the electrophotographic photosensitive member is also used for the purpose of reducing the frictional resistance and wear on the surface of the electrophotographic photosensitive member and increasing the transfer efficiency of toner from the electrophotographic photosensitive member to a transfer belt or paper. , A protective layer or the like) may contain a fluorine-based resin, a silicone resin, a polyethylene resin, or the like. Moreover, you may contain the particle | grains which consist of these resin, the particle | grains of an inorganic compound, etc.

[II-5. Formation method of each layer]
Each layer constituting these photoconductors is formed by applying the coating solution obtained by the above-described method on a support using a known coating method, repeating the coating and drying steps for each layer, and sequentially coating the layers. The

  When forming a photosensitive layer of a single-layer type photoreceptor and a charge transport layer of a function-separated type photoreceptor, the solid content concentration of the coating solution is usually 5% by weight or more, especially 10% by weight or more, and usually 40% by weight or less. Of these, the range of 35% by weight or less is preferable. Further, the viscosity of the coating solution is usually 10 mPa · s or more, preferably 50 mPa · s or more, and usually 500 mPa · s or less, preferably 400 mPa · s or less.

  When the charge generation layer of the function-separated type photoreceptor is formed, the solid content concentration of the coating solution is usually 0.1% by weight or more, especially 1% by weight or more, and usually 15% by weight or less, especially 10% or less. Is preferable. In addition, the viscosity of the coating liquid is preferably 0.01 mPa · s or more, particularly 0.1 mPa · s or more, and usually 20 mPa · s or less, particularly 10 mPa · s or less.

  Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used.

  The method for drying the coating solution is not particularly limited, but it is usually preferable to dry by heating at room temperature without touching or blowing with air. The heating temperature is in the range of 30 to 200 ° C. in particular for 1 minute to 2 hours, and the heating temperature may be constant or may be changed while drying.

[III. Image forming apparatus]
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

  As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device (charging unit) 2, an exposure device (exposure unit) 3, and a developing device (developing unit) 4. Accordingly, a transfer device 5, a cleaning device 6, and a fixing device 7 are provided.

  The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are arranged along the outer peripheral surface of the electrophotographic photoreceptor 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. Examples of the charging device include a corona charging device such as a corotron and a scorotron, a direct charging device (contact type charging device) that charges a direct charging member to which a voltage is applied by contacting the photosensitive member surface, and a contact type charging device such as a charging brush. Often used. Examples of direct charging means include contact chargers such as charging rollers and charging brushes. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2. As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Moreover, as a voltage applied at the time of charging, it is possible to use only a direct current voltage or to superimpose an alternating current on a direct current.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. .

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

  The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicone resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.

  The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed of a resin blade such as silicone resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such metal blade with resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

  The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.

  As the toner, in addition to the pulverized toner, chemical toners such as suspension granulation, suspension polymerization, and emulsion polymerization aggregation can be used. In particular, in the case of chemical toners, those having a small particle size of about 4 to 8 μm are used, and those having a shape close to a sphere, and those outside a sphere such as a potato or rugby ball can also be used. . The polymerized toner is excellent in charging uniformity and transferability, and is preferably used for high image quality.

  The type of the toner T is arbitrary, and chemical toners such as suspension granulation, suspension polymerization, and emulsion polymerization aggregation can be used in addition to powdered toner. In the case of chemical toners, those having a small particle size of about 4 to 8 μm are preferable, and the toner particles have various shapes from a nearly spherical shape to a potato shape outside the spherical shape. Can be used. In particular, the polymerized toner is excellent in charging uniformity and transferability, and is suitably used for high image quality.

  The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like that are disposed to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner. If there is little or almost no residual toner, the cleaning device 6 may be omitted.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, and a fixing sheet. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

  When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.

  The type of the fixing device is not particularly limited, and a fixing device of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

  In the image forming apparatus configured as described above, an image is recorded according to the following method (the image forming method of the present invention).

  That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed with a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

  Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

  The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.

  When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.

  After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.

  In addition to the above-described configuration, the image forming apparatus may be configured to perform, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

  The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.

  The electrophotographic photoreceptor 1 is used alone or in combination with one or more elements of the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7. And an integrated cartridge (this is appropriately referred to as an “electrophotographic photosensitive member cartridge”), and the electrophotographic photosensitive member cartridge can be attached to and detached from a main body of an image forming apparatus such as a copying machine or a laser beam printer. May be. In this case, a cartridge case configured to be detachable from the image forming apparatus is used, and the electrophotographic photosensitive member 1 is accommodated and supported by the cartridge case alone or in combination with the above-described elements. It can be. With this configuration, for example, when the electrophotographic photosensitive member 1 and other members deteriorate, the electrophotographic photosensitive member cartridge is removed from the main body of the image forming apparatus, and another new electrophotographic photosensitive member cartridge is mounted on the main body of the image forming apparatus. This facilitates maintenance and management of the image forming apparatus.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples and comparative examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

[Powder XRD spectrum measurement and peak half-width calculation conditions]
In addition, the powder X-ray-diffraction spectrum of the phthalocyanines obtained by each synthesis example mentioned later and the comparative synthesis example was measured in the following procedures. That is, as a measuring apparatus, PW1700 manufactured by PANalytical, which is a concentrated optical system powder X-ray diffractometer using CuKα characteristic X-rays (wavelength 1.541１．５) as a radiation source, was used. Measurement conditions are: X-ray output 40 kV, 30 mA, scanning range (2θ) 3-40 °, scanning step width 0.05 °, scanning speed 3.0 ° / min, divergence slit 1.0 °, scattering slit 1.0 The light receiving slit was 0.2 mm.

The peak half-width was calculated by the profile fitting method. Profile fitting was performed using powder X-ray diffraction pattern analysis software JADE5.0 + manufactured by MDI. The calculation conditions were as follows. That is, the background was fixed at an ideal position from the entire measurement range (2θ = 3.0 to 40.0 °). As the fitting function, a Peason-VII function considering the contribution of CuKα ₂ was used. Three variables of the fitting function were refined: diffraction angle (2θ), peak height, and peak half-value width (β _o ). The influence of CuKα ₂ was removed, and the diffraction angle (2θ), peak height, and peak half-value width (β _o ) derived from CuKα ₁ were calculated. The asymmetry was fixed at 0 and the shape constant was fixed at 1.5.

The peak half-value width (β _o ) calculated by the above profile fitting is the peak half width (2θ = 28.442 °) of the standard Si (NIST Si 640b) calculated by the same measurement conditions and the same profile fitting conditions. By correcting according to the following formula using β _Si ), the half width (β) derived from the sample was obtained.

[Synthesis Example 1 (β-type oxytitanium phthalocyanine crystal)]
A β-type oxytitanium phthalocyanine crystal was prepared according to the procedure of “Example of production of crude TiOPc” described in JP-A-10-7925 and then “Example 1”. The powder XRD spectrum of the obtained β-type oxytitanium phthalocyanine crystal is shown in FIG. In addition, the chlorine content contained in the obtained β-type oxytitanium phthalocyanine crystal is measured by the method described in the column <Chlorine content measurement conditions (elemental analysis)> in the above [Best Mode for Carrying Out the Invention]. As a result, the chlorine content was 0.20% by weight or less below the lower limit of detection. In addition, the peak of chlorooxytitanium phthalocyanine with respect to oxytitanium phthalocyanine in the β-type oxytitanium phthalocyanine crystal obtained in accordance with the method described in the section <Mass spectrum measurement conditions> of [Best Mode for Carrying Out the Invention] above The intensity ratio was measured and found to be 0.002.

[Synthesis Example 2 (low crystalline oxytitanium phthalocyanine)]
60 parts by weight of the β-type oxytitanium phthalocyanine crystal obtained in Synthesis Example 1 was added to 1500 parts by weight of 95% concentrated sulfuric acid cooled to −10 ° C. or lower. At this time, it added slowly so that the internal temperature of a sulfuric acid solution might not exceed -5 degreeC. After completion of the addition, the concentrated sulfuric acid solution was stirred at −5 ° C. or lower for 2 hours. After stirring, the concentrated sulfuric acid solution was filtered through a glass filter, the insoluble matter was filtered off, and then the concentrated sulfuric acid solution was released into 15000 parts by weight of ice water to precipitate oxytitanium phthalocyanine, followed by stirring for 1 hour after the release. After stirring, the solution was filtered off, and the resulting wet cake was washed again in 3000 parts by weight of water for 1 hour and filtered. By repeating this washing operation until the ionic conductivity of the filtrate reached 0.5 mS / m, 604 parts by weight of a low crystalline oxytitanium phthalocyanine wet cake was obtained (oxytitanium phthalocyanine content 9.9% by weight). . FIG. 7 shows a powder XRD spectrum of the obtained low crystalline oxytitanium phthalocyanine crystal.

[Synthesis Examples 3-31, Comparative Synthesis Examples 1-6]
As a phthalocyanine crystal precursor, 40 parts by weight of a low crystalline oxytitanium phthalocyanine wet cake obtained in Synthesis Example 2 was added to 100 parts by weight, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 9 ml of each of the contact treatment liquids of Synthesis Examples 3 to 31 shown in Table 1 (a solution obtained by mixing an amino compound with a non-amino organic compound at a predetermined concentration) was added, and the mixture was further stirred at room temperature for 1 hour. After stirring, water was separated, 80 parts by weight of methanol was added, and the mixture was stirred and washed at room temperature for 1 hour. After washing, the mixture was filtered, and 80 parts by weight of methanol was added again, followed by stirring and washing for 1 hour, followed by filtration and drying by heating in a vacuum dryer to obtain crystals composed of oxytitanium phthalocyanine alone (these are described below). This is referred to as the phthalocyanine crystal of Synthesis Examples 3 to 31 as appropriate.)

  Further, instead of the contact treatment liquids of Synthesis Examples 3 to 31, 9 ml of each of the contact treatment liquids of Comparative Synthesis Examples 1 to 6 shown in Table 1 below (liquids composed only of non-amino organic compounds or liquids composed only of amino compounds) The crystal | crystallization which consists of oxytitanium phthalocyanine single was obtained by performing operation similar to the synthesis examples 3-31 except having used (these are suitably called the phthalocyanine crystal of the comparative synthesis examples 1-6 below).

  For the phthalocyanine crystals of Synthesis Examples 3 to 31 and Comparative Synthesis Examples 1 to 6, powder XRD spectra were measured. Each of the obtained powder XRD spectra had a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to the CuKα characteristic X-ray (wavelength 1.541Å). When the non-amino organic compound used was the same, a powder X-ray diffraction spectrum having substantially the same shape was obtained regardless of the presence or absence of the amino compound. As representative examples, powder XRD spectra of the phthalocyanine crystals obtained in Synthesis Examples 3, 24, 26, 28, and 30 are shown in FIGS.

[Synthesis Example 32]
A solution obtained by dissolving 40 parts by weight of a low crystalline oxytitanium phthalocyanine (phthalocyanine crystal precursor) wet cake obtained in Synthesis Example 2 in 15 ml of anthranilic acid (amino compound) in 100 ml of tetrahydrofuran (non-amino organic compound) (below) In addition to the contact treatment solution of Synthesis Example 32 shown in Table 1, the mixture was stirred at room temperature for 3 hours. After stirring, the mixture was filtered and dried by heating in a vacuum dryer to obtain a crystal composed of oxytitanium phthalocyanine alone (hereinafter, referred to as the phthalocyanine crystal of Synthesis Example 32 as appropriate). A powder XRD spectrum of the phthalocyanine crystal of Synthesis Example 32 is shown in FIG. As is apparent from FIG. 13, the powder XRD spectrum of the phthalocyanine crystal of Synthesis Example 32 has a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to the CuKα characteristic X-ray (wavelength 1.541Å). I had it.

[Comparative Synthesis Example 7]
In the above Synthesis Example 32, the same operation as in Synthesis Example 32 was performed except that 100 ml of tetrahydrofuran (contact treatment liquid of Comparative Synthesis Example 7 shown in Table 1 below) was used instead of the tetrahydrofuran solution of anthranilic acid. A crystal made of oxytitanium phthalocyanine alone was obtained (hereinafter referred to as phthalocyanine crystal of Comparative Synthesis Example 7 as appropriate). When the powder XRD spectrum of the phthalocyanine crystal of Comparative Synthesis Example 7 was measured, the obtained powder XRD spectrum was almost the same shape as the powder XRD spectrum of the phthalocyanine crystal of Synthesis Example 32 (FIG. 13).

[Synthesis Example 33 (low crystalline phthalocyanine composition)]
60 parts by weight of the oxytitanium phthalocyanine crystal of Synthesis Example 1 used as a raw material in Synthesis Example 2 was replaced with 47.5 parts by weight of the oxytitanium phthalocyanine crystal of Synthesis Example 1 and a metal-free phthalocyanine (manufactured by Dainippon Ink & Chemicals, Inc. Fastgen Blue 8120BS ") Except for changing to a mixture with 2.5 parts by weight, the same operation as in Synthesis Example 2 was performed to obtain 410 parts by weight of a low crystalline phthalocyanine composition wet cake (content of phthalocyanines) 12.2 wt%). FIG. 14 shows a powder XRD spectrum of the obtained low crystalline phthalocyanines.

[Synthesis Examples 34 to 37, Comparative Synthesis Example 8]
As a phthalocyanine crystal precursor, 33 parts by weight of a wet cake of the low crystalline phthalocyanine composition obtained in Synthesis Example 33 was added to 90 parts by weight of water and stirred at room temperature for 30 minutes. Thereafter, 9 ml of each of the contact treatment liquids of Synthesis Examples 34 to 37 shown in Table 2 below (a solution in which an amino compound is mixed with 3-chlorobenzaldehyde, which is a non-amino organic compound) is added, and further stirred at room temperature for 1 hour. did. After stirring, water was separated, 80 parts by weight of methanol was added, and the mixture was stirred and washed at room temperature for 1 hour. After washing, the mixture was filtered, and 80 parts by weight of methanol was added again, followed by stirring and washing for 1 hour, followed by filtration and drying by heating in a vacuum dryer to obtain a mixed crystal of oxytitanium phthalocyanine and metal-free phthalocyanine ( These are referred to as phthalocyanine crystals of Synthesis Examples 34 to 37, respectively.)

  Further, instead of the contact treatment liquids of Synthesis Examples 34 to 37 described above, 9 ml of the contact treatment liquid of Comparative Synthesis Example 8 shown in Table 2 below (a liquid composed only of 3-chlorobenzaldehyde which is a non-amino organic compound) was used. Otherwise, the same operation as in Synthesis Examples 34 to 37 was performed to obtain a crystal composed of oxytitanium phthalocyanine alone (hereinafter referred to as the phthalocyanine crystal of Comparative Synthesis Example 8 as appropriate).

  With respect to the phthalocyanine crystals of Synthesis Examples 34 to 37 and Comparative Synthesis Example 8, powder XRD spectra were measured. Each of the obtained powder XRD spectra had a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to the CuKα characteristic X-ray (wavelength 1.541Å). In addition, these powder X-ray diffraction spectra were almost the same shape. As a typical example, a powder XRD spectrum of the phthalocyanine crystal obtained in Synthesis Example 34 is shown in FIG.

[Method for producing photoreceptor]
Using a conductive support in which an aluminum vapor-deposited film (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), an undercoat layer prepared by the following method on the vapor-deposited layer of the support The coating dispersion was applied with a bar coater so that the film thickness after drying was 1.25 μm or less, and dried to form an undercoat layer.

  The undercoat layer dispersion was prepared by the following method. That is, a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide were flowed at high speed Disperse the surface-treated titanium oxide obtained by mixing at high speed with a rotary mixing speed of 34.5 m / sec using a ball mill of methanol / 1-propanol. Thus, a dispersion slurry of hydrophobized titanium oxide was obtained. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (A)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula ( Compound represented by B)] / hexamethylenediamine [compound represented by the following formula (C)] / decamethylene dicarboxylic acid [compound represented by the following formula (D)] / octadecamethylene dicarboxylic acid [following formula The compound represented by (E)] has a composition molar ratio of 60% / 15% / 5% / 15% / 5% and is agitated and mixed with pellets of copolymerized polyamide to dissolve the polyamide pellets. Then, ultrasonic dispersion treatment is performed, so that the weight ratio of methanol / 1-propanol / toluene is 7/1/2, and the hydrophobically treated titanium oxide / copolymerized polymer. Containing de in a weight ratio 3/1 was undercoat layer dispersion having a solid concentration of 18.0%.

  On the other hand, 20 parts by weight of each phthalocyanine crystal to be described later was used as a charge generating substance, mixed with 280 parts by weight of 1,2-dimethoxyethane, and pulverized with a sand grind mill for 2 hours for atomization dispersion treatment. In addition, a mixture of 253 parts by weight of 1,2-dimethoxyethane and 85 parts by weight of 4-methoxy-4-methyl-2-pentanone was added to polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denkabutyral” # 6000C) 10 parts by weight was dissolved to prepare a binder liquid. A charge generation layer coating liquid was prepared by mixing the above-mentioned finely-treated liquid obtained by the above-described atomization dispersion treatment and the above-described binder liquid and 230 parts by weight of 1,2-dimethoxyethane. This charge generation layer coating solution is applied onto the undercoat layer formed on the conductive support by a bar coater so that the film thickness after drying is 0.4 μm and dried to generate charges. A layer was formed.

  Further, 50 parts by weight of a compound represented by the following structural formula (F) synthesized based on Example 1 of JP-A-2002-80432 is used as a charge transport material, and also represented by the following structural formula (G). 51 mol% of a repeating unit having 2,2-bis (4-hydroxy-3-methylphenyl) propane as an aromatic diol component, and 1,1-bis (4-hydroxyphenyl) represented by the following structural formula (H) ) 1-phenylethane is used as an aromatic diol component 49 mol% of repeating units, and 100 parts by weight of a polycarbonate resin having a terminal structural formula derived from pt-butylphenol is used as a binder resin. , 6-Di-t-butyl-4-methylphenol 8 parts by weight, silicone oil (trade name “KF96”, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.03 The amount unit, to prepare a charge transport layer coating liquid was dissolved in tetrahydrofuran / toluene (weight ratio 8/2) mixed solvent 640 parts by weight. The charge transport layer coating solution is applied onto the charge generation layer with a film applicator so that the film thickness after drying is 25 μm, and dried to form a charge transport layer, whereby a laminated photosensitive layer is formed. An electrophotographic photosensitive member was prepared.

[Examples 1 to 34, Comparative Examples 1 to 8]
Using the phthalocyanine crystals of Synthesis Examples 3 to 32 and Synthesis Examples 34 to 37 and Comparative Synthesis Examples 1 to 8 as charge generation materials, electrophotographic photoreceptors were produced in accordance with the above-described photoreceptor production method (hereinafter referred to as appropriate as follows). The electrophotographic photoreceptors of Examples 1 to 34 and Comparative Examples 1 to 8 are referred to.). The correspondence between each electrophotographic photosensitive member, the phthalocyanine crystal used as the charge generation material, and the composition thereof is shown in Tables 3 and 4 below.

[Evaluation of electrophotographic photoreceptor]
An electrophotographic characteristic evaluation apparatus manufactured according to the standards of the Electrophotographic Society using the electrophotographic photoreceptors of Examples 1 to 34 and Comparative Examples 1 to 8 ("Basic and Application of Secondary Electrophotographic Technology", edited by the Electrophotographic Society, Corona) , 404-405), and the electrical characteristics were evaluated by carrying out a cycle of charging, exposure, potential measurement, and static elimination according to the following procedure.

Under the conditions of a temperature of 25 ° C. and a humidity of 50%, the photosensitive member is charged so that the initial surface potential becomes −700 V, and the halogen lamp light is irradiated with a monochromatic light of 780 nm by an interference filter. The irradiation energy (half exposure energy) at −350 V was measured as sensitivity (hereinafter sometimes referred to as “E _1/2 ”) (unit μJ / cm ² ). Further, after setting the initial surface potential to −700 V, the surface potential after being left in a dark place for 5 seconds was measured, and the difference was defined as dark decay (hereinafter sometimes referred to as “DD”) (unit V). .

  Tables 3 and 4 below show the evaluation results of the electrical characteristics of the electrophotographic photoreceptors of Examples 1 to 34 and Comparative Examples 1 to 8. In Tables 3 and 4 below, Examples and Comparative Examples using phthalocyanine crystals obtained using the same non-amino organic compound are shown side by side.

  As is apparent from the powder XRD spectra (FIGS. 8 to 13 and 15), all of the phthalocyanine crystals of Synthesis Examples 3 to 32 and Synthesis Examples 34 to 37 and Comparative Synthesis Examples 1 to 8 used as charge generation materials are used. It was a phthalocyanine crystal having a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-ray (wavelength 1.541Å).

The electrophotographic photoreceptors of Examples 1-34 and Comparative Examples 1-8 using the phthalocyanine crystals of Synthesis Examples 3-32 and Synthesis Examples 34-37 and Comparative Synthesis Examples 1-8 as charge generating materials, Depending on the composition of the phthalocyanine crystals and the type of non-amino organic compound used during the production of the phthalocyanine crystals, seven groups (Examples 1 to 21 and Comparative Examples 1 and 2; Examples 22 and 23 and Comparative Example 3; Example 24, 25 and Comparative Example 4; Examples 26, 27 and Comparative Example 5; Examples 28, 29 and Comparative Example 6; Example 30 and Comparative Example 7; Examples 31 to 34 and Comparative Example 8) Comparing the examples and the comparative examples, the non-organic organic compound and the electrophotographic photosensitive member of the example using the phthalocyanine crystal obtained by contacting with the amino compound are the non-amino organic compound alone or aminated. Compared only the electrophotographic photosensitive member of Comparative Example using the obtained phthalocyanine crystal in contact object, is seen that excellent in both sensitivity E _1/2 and dark decay DD.

[Comparative Examples 9 and 10]
When preparing the coating solution for the charge generation layer in the above-mentioned [Method for producing photoreceptor], 20 parts by weight of the phthalocyanine crystal of Comparative Synthesis Example 1 is used as the charge generation material, and 1.25 parts by weight of aniline are used together. Other than the above, an electrophotographic photosensitive member was manufactured according to the above-mentioned procedure of [Method of manufacturing photosensitive member]. This is hereinafter referred to as the electrophotographic photoreceptor of Comparative Example 9 as appropriate.

  Further, an electrophotographic photosensitive member was produced according to the same procedure as Comparative Example 9 except that 1.25 parts by weight of anthranilic acid was used instead of 1.25 parts by weight of aniline. This is hereinafter referred to as the electrophotographic photoreceptor of Comparative Example 10 as appropriate.

For these electrophotographic photoreceptors of Comparative Examples 9 and 10, the electrical characteristics were evaluated according to the same procedure as in the electrophotographic photoreceptors of Examples 1 to 34 and Comparative Examples 1 to 8 described above.
Table 5 below shows the evaluation results of the electrical characteristics of the electrophotographic photoreceptors of Examples 1 and 4 and Comparative Examples 1, 9, and 10.

  From the above results, it is possible that the above-described effects (improvement of sensitivity and improvement of chargeability) of the phthalocyanine crystal of the present invention cannot be obtained only by adding the above-mentioned amino compound at the time of preparing the coating solution for charge generation layer. It became clear.

The phthalocyanine crystal of the present invention has an advantage that it has high sensitivity and is excellent in chargeability. Therefore, it can be suitably used as a material (particularly a charge transport material) for optoelectronic devices such as solar cells, electronic paper, and electrophotographic photosensitive members.
The electrophotographic photosensitive member, the electrophotographic photosensitive member cartridge, and the image forming apparatus of the present invention are preferably used in various fields such as copying machines, printers, faxes, and other various electrophotographic devices using electrophotographic technology. Can do.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention. The example of the powder X-ray-diffraction spectrum of low crystalline phthalocyanines is shown. The example of the powder X-ray-diffraction spectrum of low crystalline phthalocyanines is shown. The example of the powder X-ray-diffraction spectrum of amorphous phthalocyanines is shown. The example of the powder X-ray-diffraction spectrum of amorphous phthalocyanines is shown. 3 is a powder XRD spectrum of β-type oxytitanium phthalocyanine crystal obtained in Synthesis Example 1. FIG. 3 is a powder XRD spectrum of the low crystalline oxytitanium phthalocyanine obtained in Synthesis Example 2. 4 is a powder XRD spectrum of a phthalocyanine crystal (crystal of oxytitanium phthalocyanine alone) obtained in Synthesis Example 3. It is a powder XRD spectrum of the phthalocyanine crystal (crystal of oxytitanium phthalocyanine alone) obtained in Synthesis Example 24. It is a powder XRD spectrum of the phthalocyanine crystal (crystal of oxytitanium phthalocyanine alone) obtained in Synthesis Example 26. It is a powder XRD spectrum of the phthalocyanine crystal (crystal of oxytitanium phthalocyanine alone) obtained in Synthesis Example 28. 4 is a powder XRD spectrum of a phthalocyanine crystal (crystal of oxytitanium phthalocyanine alone) obtained in Synthesis Example 30. 4 is a powder XRD spectrum of a phthalocyanine crystal (crystal of oxytitanium phthalocyanine alone) obtained in Synthesis Example 32. It is a powder XRD spectrum of the low crystalline phthalocyanine composition (composition containing oxytitanium phthalocyanine and metal-free phthalocyanine) obtained in Synthesis Example 33. It is a powder XRD spectrum of the phthalocyanine crystal (mixed crystal of oxytitanium phthalocyanine and metal-free phthalocyanine) obtained in Synthesis Example 34.

Explanation of symbols

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
5 Transfer device 6 Cleaning device (cleaning part)
7 Fixing Device 41 Developing Tank 42 Agitator 43 Supply Roller 44 Developing Roller 45 Regulating Member 71 Upper Fixing Member (Fixing Roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper (paper, medium)

Claims (4)

In an electrophotographic photoreceptor having a photosensitive layer on a conductive support,
The photosensitive layer contains phthalocyanine crystals;
By contacting the amorphous phthalocyanine or the low crystalline phthalocyanine with an organic compound having no unsubstituted or substituted amino group in the presence of the primary amine compound or the secondary amine compound. It is obtained through a step of converting the crystal form, and shows a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-ray (wavelength 1.541Å), and is 26.2 ° or 28. An electrophotographic photosensitive member characterized by having no clear peak at 6 ° . The electrophotographic photosensitive member according to claim 1 ,
An electrophotographic photosensitive member cartridge comprising: a cartridge case that detachably supports the electrophotographic photosensitive member with respect to an image forming apparatus. The electrophotographic photosensitive member according to claim 1 ,
A charging unit for charging the electrophotographic photosensitive member;
Exposing the charged electrophotographic photoreceptor to form an electrostatic latent image; and
An image forming apparatus comprising: a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member. In the presence of a primary amine compound or a secondary amine compound, the crystalline form is converted by bringing an amorphous phthalocyanine or a low crystalline phthalocyanine into contact with an organic compound having no unsubstituted or substituted amino group. Obtained through the process, shows a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.2 ° with respect to CuKα characteristic X-ray (wavelength 1.541Å), and is clear at 26.2 ° or 28.6 ° A phthalocyanine crystal characterized by having no peak .

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