JP2000206715A - Electrophotographic photoreceptor and process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor superior in film strength, resistances to deposition and abrasion and scratching, by including in a photosensitive layer a polymerized compound of a hole transfer compound having two or more chain-polymerizable functional groups in the same molecule. SOLUTION: The photosensitive layer of this photoreceptor contains a compound obtained by polymerizing a hole transfer compound having >=2 chain- polymerizable functional groups in the same molecule represented by formula I in which A is a hole transfer group; each of P1 and P2 is, independently, a chain-polymerizable functional group; Z is an optionally substituted organic group; each of (a), (b), and (d) is 0 or an integer of >=1, and a+b×d>=2, and when a>=2, each of plural P1 may be the same or different, and when b>=2, each of Z and P2 may be the same or different. The hole transfer compound obtained by substituting the sites combining A and P1 and Z for H atoms is represented by formulae II or III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photosensitive members. On the other hand, organic materials such as polyvinyl carbazole, phthalocyanine, and azo pigments are noted for their advantages such as high productivity and no pollution, and they tend to be inferior in terms of photoconductive properties and durability as compared with inorganic materials. , Has become widely used.

These electrophotographic photoconductors are often used as function-separated electrophotographic photoconductors in which a charge generation layer and a charge transport layer are stacked in order to satisfy both electrical and mechanical properties. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, optical characteristics, and durability characteristics according to the electrophotographic process to be applied.

Particularly, in the case of an electrophotographic photoreceptor that is used repeatedly, the surface of the photoreceptor is electrically and electrically controlled such as charging, image exposure, toner development, transfer to paper, and cleaning.
Since a mechanical external force is directly applied, durability against them is required. Specifically, durability against abrasion and scratches on the surface due to rubbing is required, and durability against surface deterioration due to charging is also required.

Generally, the surface of an electrophotographic photosensitive member is a thin resin layer, and the characteristics of the resin are very important. In recent years, acrylic resins, polycarbonate resins, and the like have been put to practical use as resins that satisfy the above-mentioned conditions to some extent. However, not all of the above-described characteristics are satisfied by these resins, and in particular, electrophotographic photoreceptors It is difficult to say that the film hardness of the resin is sufficiently high for achieving high durability. Even when these resins are used as a resin for forming a surface layer, there is a problem in that the surface layer is worn and the flaw is further generated during repeated use.

Further, in recent years, low-molecular-weight compounds such as charge-transporting materials are often added in relatively large amounts due to demands for higher sensitivity of organic electrophotographic photoreceptors. In this case, these low-molecular-weight materials are used as plasticizers. Due to the unusual effect, the film strength is remarkably reduced, and abrasion and scratching of the surface layer at the time of further repeated use are problematic. Further, when the electrophotographic photoreceptor is stored for a long period of time, the above-mentioned low molecular weight component is precipitated, and there is a problem that the layers are separated.

As a means for solving these problems, an attempt to use a curable resin as a resin for the charge transport layer has been made.
For example, it is disclosed in JP-A-2-127652. As described above, by using a curable resin as the resin for the charge transport layer and curing and cross-linking the charge transport layer, the mechanical strength is increased, and the abrasion resistance and scratch resistance during repeated use are greatly improved. However, even if a curable resin is used, the low molecular weight component functions as a plasticizer in the binder resin to the last, so that the above-mentioned problems of precipitation and layer separation have not been fundamentally solved.

In a charge transport layer composed of an organic charge transport material and a binder resin, the charge transport ability greatly depends on the resin. For example, a curable resin having sufficiently high hardness has insufficient charge transport ability. However, there is no increase in the residual potential upon repeated use, and both have not been satisfied. In JP-A-5-216249 and JP-A-7-72640, a charge transporting layer contains a monomer having a carbon-carbon double bond, and a carbon-carbon double bond of the charge transporting material and a heat-transferring material. Alternatively, an electrophotographic photoreceptor in which a charge transport layer cured film is formed by reacting with light energy is disclosed, but the charge transport material is merely fixed in a pendant shape to the polymer main skeleton, and the plasticity of the plastic is reduced. Mechanical action cannot be sufficiently eliminated, so that the mechanical strength is not sufficient. In addition, when the concentration of the charge transporting material is increased to improve the charge transporting ability, the crosslink density becomes low and sufficient mechanical strength cannot be secured.

Another solution is disclosed in, for example,
JP-A-248649 discloses an electrophotographic photoreceptor having a charge transport layer formed by introducing a group having a charge transport ability into a thermoplastic polymer main chain. It has an effect on precipitation and layer separation compared to the transport layer, and improves mechanical strength, but it is a thermoplastic resin to the last, its mechanical strength is limited, including the solubility of the resin It is hard to say that handling and productivity are sufficient. As described above, the conventional system has not achieved both high mechanical strength and charge transport ability.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of a conventional electrophotographic photosensitive member using a resin as a surface layer, and to improve the abrasion resistance by increasing the film strength. Another object of the present invention is to provide an electrophotographic photoreceptor having improved scratch resistance and good deposition resistance.

Another object of the present invention is to provide an electrophotographic apparatus capable of exhibiting stable performance even when repeatedly used, with very little change or deterioration in electrophotographic photosensitive member characteristics such as an increase in residual potential upon repeated use. It is to provide a photoreceptor.

Still another object of the present invention is to improve the abrasion resistance and scratch resistance of the surface layer of an electrophotographic photosensitive member, to provide a long-life, high-quality electrophotographic photosensitive member, and to provide a process cartridge having the electrophotographic photosensitive member. And an electrophotographic apparatus.

[0013]

According to the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer has two or more photosensitive molecules in the same molecule represented by the following general formula (1). An electrophotographic photosensitive member containing a compound obtained by polymerizing a hole transporting compound having a chain polymerizable functional group, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus are provided.

[0014]

Embedded image

In the formula, A represents a hole transporting group. P ¹ and P ² represent a chain polymerizable functional group. P ¹ and P ² may be the same or different. Z represents an organic residue which may have a substituent. a, b and d each represent 0 or an integer of 1 or more, and a + b
Xd represents an integer of 2 or more. When a is 2 or more, P
¹ may be the same or different; when d is 2 or more, P ² may be the same or different; and when b is 2 or more, Z and P ² may be the same or different.

[0016]

Embodiments of the present invention will be described below in detail.

First, the chain polymerizable functional group in the present invention will be described. The term chain polymerization in the present invention refers to the former type of polymerization reaction when the formation reaction of a polymer is largely divided into chain polymerization and sequential polymerization.For example, for example, Gihodo Shuppan Tadahiro Miwa's `` Basic synthetic resin chemistry '' (New edition) 1
July 25, 995 (1st edition, 8th press) As described in 24, the form mainly refers to unsaturated polymerization, ring-opening polymerization, isomerization polymerization and the like in which the reaction proceeds mainly through intermediates such as radicals or ions.

The chain-polymerizable functional groups P ¹ and P ² in the general formula (1) mean functional groups capable of the above-mentioned reaction mode, and here, they occupy most of them, and have a wide range of application. Alternatively, specific examples of the ring-opening polymerizable functional group are shown.

Unsaturated polymerization refers to an unsaturated group such as CＣC, C≡C, C ＝ O, C ＝
This is a reaction in which N, C≡N and the like are polymerized, and mainly CＣC. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.

[0020]

[Table 1]

In the table, R represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. An aryl group such as a phenyl group, a naphthyl group and an anthryl group or a hydrogen atom which may be possessed.

Ring-opening polymerization is a process in which an unstable cyclic structure having a strain, such as a carbon ring, an oxo ring, or a nitrogen heterocycle, is activated by the action of a catalyst. Is generated, but in this case, most of the ions basically act as active species.
Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but are not limited thereto.

[0023]

[Table 2]

In the table, R represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. An aryl group such as a phenyl group, a naphthyl group and an anthryl group or a hydrogen atom which may be possessed.

Among the chain polymerizable functional groups according to the present invention as described above, those represented by the following general formulas (6) to (8) are preferable.

[0026]

Embedded image

In the formula, E is a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, a methyl group which may have a substituent,
Alkyl group such as ethyl group, propyl group and butyl group, benzyl group which may have a substituent, aralkyl group such as phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, and phenyl which may have a substituent; Group, naphthyl group,
Aryl groups such as anthryl group, pyrenyl group, thiophenyl group and furyl group, alkoxy groups such as CN group, nitro group, methoxy group, ethoxy group and propoxy group, -COO
R ¹⁶ or —CONR ¹⁷ R ¹⁸ is shown.

W is an arylene group such as a divalent phenylene group, a naphthylene group or an anthracenylene group which may have a substituent, or a divalent group such as a methylene group, an ethylene group or a butylene group which may have a substituent. Alkylene group, -COO-,
-O -, - OO -, - represented by S- or -CONR ^19.

Here, R ^{16 to} R ¹⁹ have a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, and a substituent. R ¹⁷ and R ¹⁷ represent an aralkyl group such as a benzyl group and a phenethyl group or an aryl group such as a phenyl group, a naphthyl group and an anthryl group which may have a substituent;
¹⁸ may be the same or different from each other. F indicates 0 or 1.

The substituents which may be present in E and W include halogen atoms such as fluorine, chlorine, bromine and iodine;
Or a nitro group or a cyano group or a hydroxyl group; or a methyl group,
Alkyl groups such as ethyl group, propyl group and butyl group; or alkoxy groups such as methoxy group, ethoxy group and propoxy group; or aryloxy groups such as phenoxy group and naphthoxy group; or benzyl group, phenethyl group, naphthylmethyl group, Aralkyl groups such as furfuryl group and thienyl group; or aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group.

[0031]

Embedded image

In the formula, R ²⁰ and R ²¹ are a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent; a benzyl group which may have a substituent; It represents an aralkyl group such as a phenethyl group or an aryl group such as a phenyl group and a naphthyl group which may have a substituent, and n represents an integer of 1 to 10.

[0033]

Embedded image

In the formula, R ²² and R ²³ are a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent; a benzyl group which may have a substituent; It represents an aralkyl group such as a phenethyl group or an aryl group such as a phenyl group and a naphthyl group which may have a substituent, and n represents 0 or an integer of 1 to 10.

The above general formulas (7) and (8)
Examples of the substituent which R ^{20 to} R ²³ may have include fluorine,
Halogen atoms such as chlorine, bromine and iodine; or alkyl groups such as methyl group, ethyl group, propyl group and butyl group; or alkoxy groups such as methoxy group, ethoxy group and propoxy group; or aryl groups such as phenoxy group and naphthoxy group An oxy group; an aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group and a thienyl group; and an aryl group such as a phenyl group, a naphthyl group, an anthryl group and a pyrenyl group.

Further, among the above general formulas (6) to (8), more preferable chain polymerizable functional groups include those represented by the following general formulas (9) to (15).

[0037]

Embedded image

Further, among the above general formulas (9) to (15), an acryloyloxy group of the general formula (9) or a methacryloyloxy group of the general formula (10) is particularly preferable from the viewpoint of polymerization characteristics and the like.

In the present invention, "a hole-transporting compound having a chain-polymerizable functional group" means that the above-mentioned chain-polymerizable group is chemically bonded to the above-described hole-transporting compound by two or more functional groups. Are shown. In this case, all of the chain polymerizable functional groups may be the same or different. The hole transporting compound having two or more of these chain polymerizable functional groups is represented by the general formula (1).

In the general formula (1), when “a is 2 or more, P¹
May be the same or different. "
Of chain polymerizable functional groups¹¹, P¹², P¹³, P¹⁴, P¹⁵
.... P¹ⁿ, For example, when a = 3, hole transport
Chain polymerizable functional group P directly bonded to transportable compound A¹Is 3
Two things are the same, but two are the same and one is different (for example,
If P¹¹And P¹¹And P¹²But all three are different
(For example, P ¹²And P¹⁵And P¹⁷Or)
(“D is 2 or more, P
^TwoMay be the same or different. "
In the case above, Z and P^TwoMay be the same or different. "
This means the same thing.)

A represents a hole transporting group, and A and P ¹
And a hydrogenated compound (hole transport compound) in which the bonding site to Z is replaced by a hydrogen atom is represented by the following general formulas (2) and (3).

[0042]

Embedded image

In the formula, m represents 0 or 1, and it is preferable that m = 1, and R ^{1 to} R ⁴ represent optionally substituted methyl, ethyl, propyl and butyl groups. Carbon number 1
0 or less alkyl group, benzyl group which may have a substituent, phenethyl group, naphthylmethyl group, aralkyl group such as furfuryl group and thienyl group or phenyl group which may have a substituent, naphthyl group, anthryl group An aryl group such as a phenanthryl group, a pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group. And R ^{1 to} R ⁴ may be the same or different.

Ar ¹ is an optionally substituted arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. From which two hydrogens have been removed)
Ar ² when m = 0, a phenyl group which may have a substituent, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, An aryl group such as a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group is shown. When m = 1, an arylene group similar to the above Ar ¹ is shown. When m = 1, Ar ¹ and A
r ² may be the same or different.

Further, among them, R in the general formula (2)
^It is preferable that ¹ and R ² are an aryl group which may have a substituent, and it is particularly preferable that all of R ^{1 to} R ⁴ are an aryl group which may have a substituent. Further, R ¹ and R ² or R ³ and R ⁴ or Ar ¹ and Ar ^{2 in} the above general formula (2)
May be bonded directly or via a bonding group. Examples of the bonding group include an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and sulfur atom, and a CHＣＨCH group. Among these, an alkylene group is preferred.

[0046]

Embedded image

In the formula, R ⁵ , R ⁶ , R ⁹ and R ¹⁰ represent an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, and a substituent. Benzyl group which may have, phenethyl group, naphthylmethyl group,
A phenyl group which may have an aralkyl group or a substituent such as a furfuryl group and a thienyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group,
R ⁵ represents an aryl group such as a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group;
R ⁶ , R ⁹ and R ¹⁰ may be the same or different. R ⁷ and R ⁸ are a methylene group which may have a substituent, an alkylene group having 10 or less carbon atoms such as an ethylene group and a propylene group, or an arylene group which may have a substituent (benzene, naphthalene, anthracene, A group obtained by removing two hydrogens from phenanthrene, pyrene, thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.), and R
⁷ and R ⁸ may be the same or different. Q represents an organic residue which may have a substituent.

Further, among them, R in the general formula (3)
⁵ , two or more of R ⁶ , R ⁹ and R ¹⁰ may be an aryl group which may have a substituent, and R ⁷ and R ⁸ may be an arylene group which may have a substituent. Preferably, further R
^It is particularly preferable that all four of R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are aryl groups which may have a substituent. Any two of R ⁵ or R ⁶ or R ^{7 in} the general formula (3) or any two of R ⁸ or R ⁹ or R ¹⁰ may be bonded directly or via a bonding group, respectively. As the bonding group, methylene group, alkylene group such as ethylene group and propylene group, hetero atom such as oxygen and sulfur atom,
CH = CH group and the like.

Z in the general formula (1) or Q in the general formula (3) represents an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ¹¹ = CR
¹² (R ¹¹ and R ¹² represent an alkyl group, an aryl group or a hydrogen atom, and R ¹¹ and R ¹² may be the same or different),
C = O, S = O, SO ₂ , an organic residue which is one or arbitrarily combined from an oxygen atom or a sulfur atom. Among them, a compound represented by the following general formula (4) is preferable, and a compound represented by the following general formula (5) is particularly preferable.

[0050]

Embedded image

[0051]

Embedded image

In the above general formula (4), X¹~ X^ThreeIs a substituent
Methylene group, ethylene group and propylene group which may have
Alkylene groups having 20 or less carbon atoms, such as (CR¹³= C
R¹⁴) M ¹, C = O, S = O, SO_Two, Oxygen atom or sulfur
Represents an atom, Ar^ThreeAnd Ar^FourIs an optionally substituted
Rylene group (benzene, naphthalene, anthracene,
Enanthrene, pyrene, thiophene, pyridine, quinoli
Benzoquinoline, carbazole, phenothiazine,
Benzofuran, benzothiophene, dibenzofuran and
Removed two hydrogen atoms from dibenzothiophene etc.
Group). R¹³And R¹⁴Is a methyl group which may have a substituent
Alkyl group such as phenyl group, ethyl group and propyl group, substituent
A phenyl group, a naphthyl group and a thiophenyl
An aryl group or a hydrogen atom such as¹³And R¹⁴
May be the same or different. m¹Is an integer of 1 to 5, p to
t represents 0 or an integer of 1 to 10 (provided that p to t are
It cannot be 0).

In the above general formula (5), X ⁴ and X ⁵ represent (CH
₂ ) _g , (CH ＝ CR ¹⁵ ) _h , C ＝ O, or an oxygen atom, and Ar ⁵ is an arylene group which may have a substituent (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, A group obtained by removing two hydrogen atoms from quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, and the like. R ¹⁵
Represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group and a thiophenyl group which may have a substituent, or a hydrogen atom. g is an integer of 1 to 10, h is an integer of 1 to 5, u to w is an integer of 0 or 1 to 10 (particularly preferably 0 or an integer of 1 to 5; It cannot be 0).

It should be noted that R ^{1 in the} above general formulas (1) to (5)
-R ¹⁵ , Ar ¹ -Ar ⁵ , X ¹ -X ⁵ , Z and Q each may have a substituent such as a halogen atom such as fluorine, chlorine, bromine and iodine; or a nitro group or a cyano group or Hydroxyl group; or alkyl group such as methyl group, ethyl group, propyl group and butyl group; or alkoxy group such as methoxy group, ethoxy group and propoxy group; or aryloxy group such as phenoxy group and naphthoxy group; or benzyl group, phenethyl Aralkyl groups such as a group, naphthylmethyl group, furfuryl group and thienyl group; or aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group;
Or a substituted amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group and a di (p-tolyl) amino group; or an arylvinyl group such as a styryl group and a naphthylvinyl group.

In the present invention, the hole transporting compound having two or more chain-polymerizable functional groups in the same molecule preferably has an oxidation potential of 1.2 (V) or less.
More preferably, it is 4 to 1.2 (V). that is,
When the oxidation potential exceeds 1.2 (V), it is difficult to inject charges (holes) from the charge generation material, and problems such as an increase in residual potential, deterioration in sensitivity, and a large potential fluctuation during repeated use are likely to occur. When the voltage is less than 0.4 (V), the compound itself is easily oxidized and deteriorates easily, in addition to the problem such as a decrease in charging ability, resulting in deterioration of sensitivity, image blur, and potential fluctuation during repeated use. This is because problems such as an increase in size are likely to occur.

The oxidation potential described here is measured by the following method.

(Measurement method of oxidation potential) A saturated calomel electrode was used as a reference electrode, and 0.1 N (n-Bu) ₄ N ⁺ ClO was used as an electrolyte.
_{Using a 4} ^- acetonitrile solution, sweep the potential applied to the working electrode (platinum) with a potential sweeper,
The potential when the obtained current-potential curve showed a peak was defined as the oxidation potential. In detail, the sample is 0.1N (n-B
^{_{u) 4 N + ClO 4 -}} 5~10mmo in acetonitrile solution
Dissolve to a concentration of about 1%. Then, a voltage is applied to this sample solution by a working electrode, and a current change when the voltage is linearly changed from a low potential (0 V) to a high potential (+1.5 V) is measured to obtain a current-potential curve. In this current-potential curve, the potential at the peak top when the current value showed a peak (the first peak when there were a plurality of peaks) was defined as the oxidation potential.

Further, the hole transporting compound having a chain polymerizable functional group has a hole transporting ability of 1 × 10 ⁻⁷ (cm ^2).
/ V. sec) or more having a drift mobility of not less than (sec.) (provided electric field: 5 × 10 ⁴ V / cm).
If the density is less than 1 × 10 ⁻⁷ (cm ² /V.sec), there is a problem that, as an electrophotographic photoreceptor, holes cannot move sufficiently before development after exposure, sensitivity is apparently reduced and residual potential is increased. May occur.

Representative examples of the hole transporting compound having a chain polymerizable functional group according to the present invention are shown below, but the invention is not limited thereto.

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

In the present invention, a typical method for synthesizing a hole transporting compound having a chain polymerizable functional group is shown below.

(Synthesis Example 1: Synthesis of Compound No. 1-24) The compound was synthesized according to the following route.

[0102]

Embedded image

1 (50 g: 0.123 mol), 2 (6
2.4 g: 0.369 mol), anhydrous potassium carbonate (2
5.5 g) and copper powder (32 g) together with 200 g of 1,2-dichlorobenzene at 180 to 190 ° C. under heating and stirring for 18 hours.
Time went. After filtering the reaction solution, the solvent was removed under reduced pressure,
The residue was recrystallized twice with a mixed solvent of toluene / methanol to obtain 60.2 g of 3.

N, N-dimethylformamide (DM
F) After cooling 242 g to 0 to 5 ° C.,
(4.8 g: 553.2 mmol) was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after dropping,
A solution of 3 (45.0 g: 92.2 mmol) in 135 g of DMF was slowly added dropwise. After completion of the dropwise addition, the mixture is stirred for 30 minutes, then returned to room temperature, stirred for 2 hours, and further heated to 80 to 85 ° C.
And stirred for 8 hours. The reaction solution was poured into about 15% aqueous sodium acetate solution (2.5 kg) and stirred for 12 hours. After neutralization, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 40.5 g of 4.

Dry tetrahydrofuran (THF) 100
0.89 g of lithium aluminum hydride was added to the mixture, and the mixture was stirred at room temperature. 4 (37 g: 68 mmol)
/ 600 ml of dry THF solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours and then 5% hydrochloric acid aqueous solution 500 m
1 was slowly added dropwise. After completion of the dropwise addition, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to give 5 to 2,
6.3 g were obtained.

5 (20 g: 36 mmol) and triethylamine (12.8 g: 126 mol) were added to dry THF.
After adding to 130 ml and cooling to 0 to 5 ° C, acryloyl chloride (9.8 g: 108 mmol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column to give 11.2 g of 6 (Compound No. 1-24) (oxidation potential: 0.80 V).

(Synthesis Example 2: Synthesis of Compound No. 1-78) The compound was synthesized according to the following route.

[0108]

Embedded image

7 (50 g: 0.172 mol), 8 (1
4.4 g: 0.069 mol), anhydrous potassium carbonate (3
6 g) and copper powder (33 g) were heated and stirred at 180 to 190 ° C. for 15 hours together with 120 g of 1,2-dichlorobenzene. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to give 9
8.5 g were obtained.

9 (25 g: 47 mmol) was added to 250 g of methylcellosolve, and sodium methylate (25 g) was slowly added with stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and further heated and stirred at 70 to 80 ° C. for 12 hours. The reaction solution was poured into water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified with a silica gel column to give 17.8 g of 10.

10 (15 g: 40 mmol) and triethylamine (14 g: 139 mmol) were added to dry T
After adding to 100 ml of HF and cooling to 0 to 5 ° C., acryloyl chloride (10.9 g: 120 mmol) was slowly added dropwise. After the completion of dropping, slowly return to room temperature, and leave at room temperature for 4 hours.
Stirring was performed for hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was subjected to column purification using a silica gel column to obtain 11.9 g of 11 (Compound No. 1-78) (oxidation potential: 0.78 V).

(Synthesis Example 3: Synthesis of Compound No. 2-33) The compound was synthesized according to the following route.

[0113]

Embedded image

1 (70 g: 0.35 mol), 2 (98
g: 0.42 mol), anhydrous potassium carbonate (73 g) and copper powder (111 g) were mixed with 1,2-dichlorobenzene 600.
The resulting mixture was heated and stirred at 180 to 190 ° C. for 10 hours together with g. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 36.2.
g was obtained.

3 (80 g: 0.26 mol) was converted to N, N-
Ethanethiol sodium salt (about 90%: 62 g) while stirring at room temperature in 300 g of dimethylformamide
Was slowly added. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and further heated and stirred under reflux for 3 hours. After cooling, the reaction solution was poured into water, made weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, and the organic layer was further extracted with a 1.2 N aqueous sodium hydroxide solution.The aqueous layer was made acidic with dilute hydrochloric acid, extracted with ethyl acetate, and dried. After drying over sodium sulfate, the solvent was removed under reduced pressure. The residue was purified with a silica gel column to give 64 g of 4.

4 (60 g: 0.21 mol) was converted to N, N-
Caustic soda (8.3 g) was slowly added to 300 g of dimethylformamide while stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 30 minutes, and 1,2-diiodoethane (31.7 g: 0.1 mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and further heated and stirred at 70 ° C. for 5 hours. The reaction solution was poured into water and extracted with toluene. The organic layer was further washed with water, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified with a silica gel column to give 49.1 g of 5.

After cooling 182 g of DMF to 0 to 5 ° C., 63.6 g of phosphorus oxychloride was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after the completion of dropping, 5 (4
(2.2 g: 0.07 mol) / 102 g DMF solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes, returned to room temperature, stirred for 2 hours, and further heated to 80 to 85 ° C.
Stirring was performed for hours. The reaction solution was poured into 1.5 kg of a 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralizing it, extraction was performed with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified by column using a silica gel column to obtain 23 g of 6.

0.89 g of lithium aluminum hydride was added to 100 ml of dry THF, and the mixture was stirred at room temperature. 6 (15 g: 0.023 mol) / 100 ml of dry THF
ml solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours, and 200 ml of a 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of the dropwise addition, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was subjected to column purification using a silica gel column to obtain 13.6 g of 7.

7 (10 g: 0.015 mol) and triethylamine (6.1 g: 0.06 mol) were added to dry TH.
After adding to 120 ml of F and cooling to 0 to 5 ° C., acryloyl chloride (4.1 g: 0.045 mol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was subjected to column purification using a silica gel column to obtain 6.4 g of 8 (Compound No. 2-33) (oxidation potential: 0.78 V).

(Synthesis Example 4: Synthesis of Compound No. 2-44) The compound was synthesized according to the following route.

[0121]

Embedded image

Diphenylchlorophosphine (80.0)
g: 0.36 mmol) in 600 ml of diethylene glycol dimethyl ether and 8 ml of water, and then oily sodium hydride (60%: 23 g: 0.58
mol) was added slowly. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and then 9 (80 g: 0.28 mol) / TH
F100 ml solution was slowly added dropwise. 80 after dropping
Heating and stirring were performed at 150C for 15 hours. After cooling, the reaction solution was poured into water, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column to give 58.5 g of 10. The synthesis method of Nos. 10 to 13 was performed according to the synthesis method of Nos. 5 to 8 of Synthesis Example 3 above to obtain 13 (Compound No. 2-44) (oxidation potential: 0.78 V).

(Synthesis Example 5: Synthesis of Compound No. 2-89) 7 (10 g: 15 mmol) obtained in the above Synthesis Example 3
l) was added to 50 ml of dry THF, and after cooling to 0 to 5 ° C., 1.8 g of oily sodium hydride (about 60%) was slowly added. After the addition is completed, return to room temperature and stir for 1 hour.
After cooling to ５5 ° C., allyl bromide (7.5 g: 0.0
62 mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour and then returned to room temperature, and the mixture was heated and stirred at 60 to 70 ° C for 3 hours. The reaction solution was poured into water, neutralized, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column to give the desired compound (Compound No. 2-89) in 5.
4 g were obtained (oxidation potential 0.76 V).

In the present invention, the compound having the hole transporting ability in the photosensitive layer is formed by polymerizing the hole transporting compound having two or more chain polymerizable functional groups in the same molecule. A three-dimensional crosslinked structure is formed with the above crosslinking points. The hole transporting compound can be polymerized or crosslinked alone or mixed with a compound having another chain polymerizable group, and the type / ratio thereof is all arbitrary. The compound having another chain polymerizable group as referred to herein includes both monomers and oligomers / polymers having a chain polymerizable group.

When the functional group of the hole transporting compound and the functional group of the other chain polymerizable compound are the same group or a group capable of polymerizing with each other, the two groups have a copolymerized three-dimensional cross-linked structure via a covalent bond. It is possible to take When the two functional groups are functional groups that do not polymerize with each other, the photosensitive layer may be a mixture of two or more three-dimensional cured products or a three-dimensional cured product of the main component in which another chain-polymerizable compound monomer or its monomer is present. Although it is configured as containing a cured product, its compounding ratio /
By properly controlling the film forming method, IPN (I
internet Penetrating Network)
That is, it is possible to form a mutual intrusion network structure.

Further, a photosensitive layer is formed from the above-mentioned hole transporting compound and a monomer or oligomer / polymer having no chain polymerizable group or a monomer or oligomer / polymer having a polymerizable group other than chain polymerizable group. May be.

Further, in some cases, it is possible to contain a hole transporting compound which is not chemically incorporated into the three-dimensional crosslinked structure, that is, has no chain polymerizable functional group. Further, other various additives, lubricants such as fine particles of fluorine atom-containing resin and the like may be contained.

The structure of the electrophotographic photoreceptor of the present invention has a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated in this order on a conductive support. , Or a single-layer structure in which a charge generation material and a charge transport material are dispersed in the same layer. In the former laminated type, the charge transport layer may have two or more layers, and in the latter single layer type, a charge transport layer may be further formed on the photosensitive layer containing the same charge generation material and charge transport material. Further, a protective layer can be formed on the charge generation layer or the charge transport layer.

In any of these cases, if the photosensitive layer contains one or both of the above-mentioned hole transporting compound having a chain polymerizable group and the one obtained by polymerizing or crosslinking the above hole transporting compound, and curing. Good. However, in view of the characteristics as an electrophotographic photoreceptor, in particular, electrical characteristics such as residual potential and durability, a function-separated type photoreceptor having a charge generation layer / charge transport layer laminated in this order is preferable. An advantage is that the surface layer can have high durability without lowering the charge transporting ability.

Next, a method for producing an electrophotographic photosensitive member according to the present invention will be specifically described.

The support of the electrophotographic photoreceptor may be any one having conductivity, for example, aluminum,
A metal or alloy such as copper, chromium, nickel, zinc and stainless steel formed into a drum or sheet, a metal foil such as aluminum and copper laminated on a plastic film, a plastic film made of aluminum, indium oxide and tin oxide And a metal provided with a conductive layer by applying a conductive material alone or together with a binder resin, and a plastic film and paper.

In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support. The undercoat layer improves the adhesiveness of the photosensitive layer, improves coating properties,
The protective layer is formed for protecting the support, covering defects on the support, improving the charge injection property from the support, and protecting the photosensitive layer against electrical breakdown.

Examples of the material of the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, Glue and gelatin are known. These are dissolved in a suitable solvent and applied on a support. At this time, the film thickness is set to 0.
1-2 μm is preferred.

When the electrophotographic photosensitive member of the present invention is a function-separated type electrophotographic photosensitive member, a charge generation layer and a charge transport layer are laminated. Examples of the charge generation material used for the charge generation layer include selenium-tellurium, pyrylium, and thiapyrylium dyes, and various kinds of central metals and crystal systems, specifically, for example, α, β, γ, ε, and X-type crystals. Phthalosinine compounds having a type, anthantrone pigments, dibenzopyrene quinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanines and JP-A No. 54-143645. Amorphous silicon and the like.

In the case of a function-separated type electrophotographic photoreceptor, the charge generation layer comprises a homogenizer, an ultrasonic dispersion, a ball mill, a vibrating ball mill, a sand mill, an atomizer, and the like. It is well dispersed by a method such as a lighter and a roll mill, coated with a dispersion, and dried, or formed as a film of a single composition such as a vapor-deposited film of the charge generation material. The film thickness is preferably 5 μm or less, especially 0.1 to 2 μm
Is preferably within the range.

When a binder resin is used, for example, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate, methacrylate, vinylidene fluoride and trifluoroethylene, polyvinyl alcohol, polyvinyl alcohol Acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin,
Phenol resins, melamine resins, silicon resins, epoxy resins, and the like.

The hole transporting compound having a chain polymerizable functional group according to the present invention may be a charge transporting layer comprising a charge transporting material and a binder resin on the charge generating layer or on the charge generating layer. Can be used as a surface protective layer having a hole transporting ability (this surface protective layer is also a photosensitive layer because it has a hole transporting ability). In any case, the method for forming the surface layer is generally to carry out a polymerization / crosslinking reaction after applying the solution containing the hole transporting compound, but the solution containing the hole transporting compound is used in advance. It is also possible to form a surface layer using, for example, a material obtained by reacting to obtain a cured product and then dispersing or dissolving in a solvent again. As a method of applying these solutions, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method, and the like are known, but a dip coating method is preferable from the viewpoint of efficiency and productivity. In addition, vapor deposition, plasma, and other known film forming methods can be appropriately selected.

In the present invention, the hole transporting compound having a chain polymerizable group is preferably polymerized and cross-linked by radiation. The greatest advantage of polymerization by radiation is that it does not require a polymerization initiator, which makes it possible to produce a very high-purity three-dimensional photosensitive layer matrix and ensures good electrophotographic properties. . In addition, the productivity is high due to the short-time and efficient polymerization reaction.Furthermore, due to the good radiation permeability, curing inhibition when the film is thick or when shielding materials such as additives are present in the film. Is very small. However, depending on the type of the chain polymerizable group and the type of the central skeleton, the polymerization reaction may not easily proceed, and in that case, the polymerization initiator can be added within a range that does not affect the polymerization reaction. The radiation used at this time is an electron beam and γ-ray.

As an accelerator for electron beam irradiation,
Any type such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used. When irradiating with an electron beam, the irradiation conditions are very important for the electrophotographic photoreceptor of the present invention to develop electrical characteristics and durability. In the present invention, the acceleration voltage is preferably 300 KV or less, and optimally 1 KV.
50 KV or less. The dose is preferably 1 Mr
ad to 100Mrad, more preferably 3Mr
It is in the range from ad to 50 Mrad. Acceleration voltage is 300
When it exceeds KV, the damage of the electron beam irradiation on the characteristics of the electrophotographic photosensitive member tends to increase. The dose is 1 Mr
Care should be taken when the amount is smaller than ad, since crosslinking tends to be insufficient, and when the dose exceeds 100 Mrad, the characteristics of the electrophotographic photosensitive member are likely to deteriorate.

When the hole transporting compound having a chain polymerizable group is used as the charge transporting layer, the amount of the hole transporting compound is based on the total mass of the charge transporting layer film after polymerization and crosslinking. The hydrogenated product of the hole transporting group A having a chain polymerizable functional group represented by the general formula (1) is preferably 20% by mass or more, and particularly preferably 40% by mass or more. If it is less than that, the charge transporting ability is reduced, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. In this case, the film thickness of the charge transport layer is preferably from 1 to 50 μm, and particularly preferably from 3 to 30 μm.

When the above-described hole transporting compound is used as a surface protective layer on the charge generating layer / charge transporting layer, the underlying charge transporting layer is made of a suitable charge transporting material, for example, poly-N
-A polymer compound having a heterocyclic or condensed polycyclic aromatic such as vinylcarbazole, polystyrylanthracene, or pyrazoline, imidazole, oxazole, triazole,
Suitable are heterocyclic compounds such as carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, low molecular weight compounds such as phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives and hydrazone derivatives. A solution obtained by dispersing / dissolving in a solvent together with a suitable binder resin (which can be selected from the above-described resins for the charge generation layer) can be applied and dried by the above-described known method.

In this case, the ratio of the charge transporting material to the binder resin is preferably 30 to 100, more preferably 50 to 100, when the total weight of both is 100, more preferably 50 to 100. You. If the amount of the charge transporting material is less than that, the charge transporting ability is reduced, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. The total thickness of the charge transport layer including the upper surface protective layer is 1
決定 50 μm, preferably 5-30 μm
m.

In the present invention, in any of the above cases, the charge transporting material can be contained in the photosensitive layer containing the cured product of the hole transporting compound.
In the case of a single-layer type photosensitive layer, the charge-generating material is simultaneously contained in the solution containing the hole-transporting compound, and the solution may be provided with an appropriate undercoat layer or an intermediate layer.
The case where the polymer is formed by polymerization and crosslinking after coating on the conductive support, and the case where the hole transport is performed on the single-layer photosensitive layer composed of the charge generation material and the charge transport material provided on the conductive support. Any of the methods of polymerizing and cross-linking after applying the solution containing the acidic compound is possible.

Various additives can be added to the photosensitive layer in the present invention. The additive is a deterioration inhibitor such as an antioxidant and an ultraviolet absorber, a lubricant such as fine particles of a fluorine atom-containing resin, and the like.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated around a shaft 2 in a direction indicated by an arrow at a predetermined peripheral speed. In the rotation process, the peripheral surface of the electrophotographic photoreceptor 1 is uniformly charged at a predetermined positive or negative potential by the primary charging means 3, and then the photosensitive member 1 is exposed to light from exposure means (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 is received. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.

The formed electrostatic latent image is then transferred to developing means 5
, And the developed toner image is taken out from a paper supply unit (not shown) between the electrophotographic photosensitive member 1 and the transfer means 6 in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed. The image is sequentially transferred to the transfer material 7 by the transfer unit 6.

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

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

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

When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal. Scanning, LED
Light emitted by driving the array, driving the liquid crystal shutter array, and the like.

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

[0153]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. In addition, "part" shows a mass part.

Example 1-1 First, a paint for a conductive layer was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide,
Phenol resin 25 parts, methyl cellosolve 20 parts, methanol 5 parts and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 300
0) It was prepared by dispersing 0.002 parts in a sand mill using φ1 mm glass beads for 2 hours. 30 of this paint
It was applied on an aluminum cylinder of mmφ by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare a coating for an intermediate layer. This paint was applied on the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

Next, 5 parts of a bisazo pigment represented by the following structural formula (16), 2 parts of a polyvinyl butyral resin and 35 parts of cyclohexanone were dispersed for 24 hours in a sand mill using φ1 mm glass beads, and tetrahydrofuran was further added. This was used as a paint for a charge generation layer. This paint is applied on the intermediate layer by a dip coating method,
Drying was performed at 15 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.2 μm.

[0157]

Embedded image

Next, Compound Example Nos. 60 parts of the hole transporting compound of 1-24 was dissolved in a mixed solvent of 30 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a paint for a charge transport layer. This paint is coated on the charge generation layer, and irradiated with an electron beam under the conditions of an acceleration voltage of 150 KV and a dose of 25 Mrad to cure the resin to form a charge transport layer having a thickness of 15 μm to obtain an electrophotographic photoreceptor. Was.

The produced electrophotographic photoreceptor was evaluated for its sedimentability with time, electrophotographic characteristics, and durability. With respect to the sedimentability with time, a urethane rubber cleaning blade for a copying machine was pressed against the surface of the photoreceptor, stored at 75 ° C., and an accelerated test for the sedimentability was performed. After 14 days, the surface of the electrophotographic photosensitive member was observed with a microscope to determine the presence or absence of precipitation. When there was no precipitation, the test was continued until further 30 days later.

The electrophotographic characteristics and durability were evaluated by mounting this electrophotographic photosensitive member on an LBP-SX manufactured by Canon Inc. and evaluating the electrophotographic characteristics and durability. The initial electrophotographic characteristics [dark potential Vd, light decay sensitivity (light amount required to attenuate light to -150 V at dark portion potential -700 V setting) and residual potential Vsl (light amount three times the light decay sensitivity) were applied. Potential), a 10,000-sheet paper-pass durability test was performed, and the occurrence of image defects was visually observed.
The shaving amount of the electrophotographic photosensitive member and the electrophotographic characteristics after the endurance were measured, and the respective change values ΔVd and ΔVl (when the same amount of light as the amount of light at which Vl became −150 V initially was irradiated after the endurance, Vl) and ΔVsl.

The results are shown in Table 3. The electrophotographic photosensitive member of the present invention did not precipitate, had good electrophotographic properties, had a small amount of abrasion in durability, and had good electrophotographic properties in durability. Shows very stable and good characteristics such that almost no change is observed.

(Examples 1-2 to 1-18) Example 1-1
In the hole transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that 1-24 was replaced with the compound shown in Table 4. Table 3 shows the results.

(Example 1-19) The compound having the hole transporting compound No. 1 in Example 1-1 was used. The amount of 1-24 was 48 parts, and an acrylic monomer represented by the following structural formula (17) was added to 1
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1 except that 2 parts were added. Table 3 shows the results.

[0164]

Embedded image

(Example 1-20) In Example 1-2, the hole transporting compound No. The amount of 1-25 was 48 parts, and an acrylic monomer represented by the following structural formula (18) was added to 1 part.
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-2 except that 2 parts were added. Table 3 shows the results.

[0166]

Embedded image

Example 1-21 In Example 1-1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that the amount of 1-24 was 48 parts and further 12 parts of an acrylic oligomer represented by the following structural formula (19) was added. Table 3 shows the results.

[0168]

Embedded image

(Examples 1-22 to 1-26) Example 1-
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that the electron beam irradiation conditions in Table 1 were changed as shown in Table 5. As a result, although the scraping amount and the durability were good, the sensitivity was slightly lowered and the residual potential was slightly increased in the initial electrophotographic characteristics by increasing the dose. Table 3 shows the results.

(Example 1-27) After forming the charge generation layer in Example 1-1, 20 parts of a styryl compound represented by the following structural formula (20) and a repeating unit represented by the following structural formula (21) were added. A charge transport layer was formed on the charge generation layer using a charge transport layer paint prepared by dissolving 10 parts of a polycarbonate resin having the same in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane. At this time, the thickness of the charge transport layer was 10 μm.

[0171]

Embedded image

[0172]

Embedded image

Next, the hole transporting compound No. 1-24
60 parts were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating for a surface protective layer. This paint is applied on the previous charge transport layer by a spray coating method, and the acceleration voltage is 150 KV and the dose is 25 M.
The resin is cured by irradiating an electron beam under the conditions of rad, and the film thickness is 5
A μm surface protective layer was formed to obtain an electrophotographic photosensitive member. This electrophotographic photosensitive member was evaluated in the same manner as in Example 1-1. Table 3 shows the results.

(Example 1-28) In Example 1-27, the compound having the hole transporting compound No. Compound No. 1-24 to Compound No. 1-
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-27 except that 28 was used. Table 3 shows the results.

Example 1-29 In Example 1-27, the compound having the hole-transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-27, except that 1 to 24 was 30 parts and 30 parts of an acrylic monomer represented by the structural formula (17) was added. Table 3 shows the results.

(Example 1-30) In Example 1-27, the compound having the hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-27, except that 1 to 24 was 30 parts and the acrylic oligomer represented by the structural formula (19) was used. Table 3 shows the results.

[0177]

[Table 3]

[0178]

[Table 4]

[0179]

[Table 5]

Example 2-1 In Example 1-1, the hole transporting compound No. Compound No. 1-24 to Compound No. 2-90
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that Example 1 was replaced. Table 6 shows the results.

(Examples 2-2 to 2-23) Example 2-1
In the hole transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1 except that 2-90 was replaced with the compound shown in Table 7. Table 6 shows the results.

(Example 2-24) The compound having the hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that the amount of 2-90 was changed to 48 parts and further 12 parts of an acrylic monomer represented by the structural formula (17) was added. Table 6 shows the results.

(Example 2-25) The compound having the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that the amount of 2-32 was 48 parts and further 12 parts of an acrylic monomer represented by the structural formula (18) were added. Table 6 shows the results.

(Example 2-26) The compound having the hole-transporting compound No. The amount of 2-90 was 48 parts, and the acrylic oligomer represented by the structural formula (19) was further added to 12 parts.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except for the addition of part. Table 6 shows the results.

(Examples 2-27 to 2-31) Example 2-
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1, except that the irradiation conditions of the electron beam in Table 1 were changed as shown in Table 8. As a result, although the scraping amount and the durability were good, the sensitivity was slightly lowered and the residual potential was slightly increased in the initial electrophotographic characteristics by increasing the dose. Table 6 shows the results.

(Example 2-32) After forming the charge generation layer in Example 2-1, a polycarbonate having 20 parts of a styryl compound represented by the structural formula (20) and a repeating unit represented by the structural formula (21) A charge transport layer was formed on the charge generation layer using a charge transport layer paint prepared by dissolving 10 parts of a resin in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane. At this time, the thickness of the charge transport layer was 10 μm.

Next, the hole transporting compound No. 2-90
60 parts were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating for a surface protective layer. This paint is applied on the previous charge transport layer by a spray coating method, and the acceleration voltage is 150 KV and the dose is 25 M.
The resin is cured by irradiating an electron beam under the conditions of rad, and the film thickness is 5
A μm surface protective layer was formed to obtain an electrophotographic photosensitive member. This electrophotographic photosensitive member was evaluated in the same manner as in Example 2-1. Table 6 shows the results.

(Example 2-33) In Example 2-32, the compound having the hole-transporting compound No. Compound No. 2-90 as Compound No. 2-
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-32 except that 91 was used. Table 6 shows the results.

(Example 2-34) In Example 2-32, the compound having the hole-transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-32 except that 30 parts of 2-90 was used and 30 parts of an acrylic monomer represented by Structural Formula (17) was added. Table 6 shows the results.

(Example 2-35) In Example 2-32, the compound having the hole-transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-32, except that 30 parts of 2-90 was used and the acrylic oligomer represented by the structural formula (19) was used. Table 6 shows the results.

[0191]

[Table 6]

[0192]

[Table 7]

[0193]

[Table 8]

(Comparative Example 1) After forming the charge generation layer in Example 1-1, 15 parts of a styryl compound represented by the structural formula (20) and polymethyl having a repeating unit represented by the following structural formula (22) Using a coating material for a charge transport layer prepared by dissolving 15 parts of a methacrylate resin in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane, the composition is applied on the charge generation layer, and dried at 110 ° C. for 1 hour. A charge transport layer was formed. At this time, the thickness of the charge transport layer was 15 μm.

[0195]

Embedded image

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1-1. As a result, precipitation was observed after 14 days. On the other hand, the electrophotographic characteristics in the initial stage were good, but the amount of shaving of the surface layer in durability was large, and image defects such as fogging and scratches occurred. Further, after 8000 sheets, the thickness of the charge transport layer was reduced due to scraping, and poor charging occurred, making image formation impossible. Table 9 shows the results.

Comparative Example 2 In Comparative Example 1, the structural formula (2
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 1 except that the polycarbonate resin represented by the structural formula (21) was used instead of the polymethyl methacrylate resin represented by 2). Precipitation was observed. In addition, although the durability was slightly improved as compared with the case of the polymethyl methacrylate resin, it was not sufficient, and image defects also occurred after the durability. Table 9 shows the results.

Comparative Example 3 In Comparative Example 2, the structural formula (2
0) and 10 parts of the styryl compound represented by the structural formula (2)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2 except that the polycarbonate resin shown in 1) was used in an amount of 15 parts. , The charge transport ability was reduced, and the sensitivity was reduced and the residual potential was increased. As a result, a ghost was observed in the image. Table 9 shows the results.

(Comparative Example 4) After forming the charge transport layer in Example 1-27, 10 parts of the styryl compound represented by the structural formula (20) and 15 parts of the polycarbonate resin represented by the structural formula (21) were converted to monochlorobenzene. It was dissolved in a mixed solvent of 50 parts / 30 parts of dichloromethane to prepare a coating for a surface protective layer. This paint was applied onto the charge transport layer by a spray coating method, and dried at 120 ° C. for 1 hour to form a surface protective layer having a thickness of 5 μm. Comparative Example 3
On the other hand, since the charge transporting layer having high charge transporting ability is in the lower layer, the sensitivity is lowered, the residual potential is slightly increased, and the shaving amount is improved, but the image after the durability still has scratches / fog. Therefore, sufficient durability could not be secured. Table 9 shows the results.

Comparative Example 5 The hole-transporting compound No. in Example 1-1 was prepared. JP-A-5-21 instead of 1-24
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that the compound represented by the following structural formula (23) disclosed in JP-A-6249 was used. As a result, the initial electrophotographic properties were good, but the durability was significantly lower than that of Example 1-1. Table 9 shows the results.

[0201]

Embedded image

Comparative Example 6 The hole transporting compound No. in Example 1-19 was used. Instead of 1-24, the structural formula (2
Example 1-19 except that the compound shown in 3) was used.
An electrophotographic photoreceptor was prepared in the same manner as described above and evaluated. As a result, the electrophotographic characteristics in the initial stage were good, but Examples 1-19.
The durability was greatly reduced as compared with. Table 9 shows the results.

(Comparative Example 7) After the charge generation layer was formed in Example 1-1, the charge generation layer was formed as described in JP-A-8-248649.
Polycarbonate resin 20 represented by the following structural formula (24) synthesized according to the production method described in Nos. 10 to 11
A charge transport layer was formed on the charge generation layer using a charge transport layer paint prepared by dissolving the above-mentioned parts in 80 parts of tetrahydrofuran. At this time, the thickness of the charge transport layer was 15 μm. The electrophotographic photoreceptor was evaluated in the same manner as in Example 1-1. As a result, although the mechanical strength was improved as compared with Comparative Examples 1 and 2, sufficient durability could not be secured. Table 9 shows the results.

[0204]

Embedded image

[0205]

[Table 9]

[0206]

As described above, the electrophotographic photoreceptor of the present invention has a
It has an effect of excellent abrasion resistance and scratch resistance. Further, the electrophotographic characteristics such as sensitivity and residual potential are very good, and stable performance can be exhibited even when repeatedly used. Further, the effect of the electrophotographic photosensitive member is naturally exerted also in a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member, and high image quality is maintained for a long time.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

[Description of Signs] 1 electrophotographic photoreceptor 2 axis 3 charging means 4 exposure light 5 developing means 6 transfer means 7 transfer material 8 fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge 12 rail

Claims (21)

[Claims] 1. An electrophotographic apparatus having a photosensitive layer on a conductive support.
In the true photoreceptor, the photosensitive layer is represented by the following general formula (1).
Having two or more chain-polymerizable functional groups in the same molecule
Containing a compound obtained by polymerizing a hole transporting compound.
An electrophotographic photosensitive member characterized by the following. Embedded image｛(Wherein A represents a hole transporting group;¹And P^TwoIs a chain
Indicates a polymerizable functional group; P ¹And P^TwoMay be the same or different
Z represents an organic residue which may have a substituent; a, b
And d represent 0 or an integer of 1 or more, and a + b × d represents 2 or more.
The above integer; and when a is 2 or more, P¹Are the same
May be different, and when d is 2 or more, P^TwoAre the same but different
And when b is 2 or more, Z and P^TwoIs the same
A and P may be different.¹The bond site with Z and Z to a hydrogen atom
The obtained hole transporting compound is represented by the following general formula (2) or
This is indicated by (3). Embedded image(Where R¹, R^Two, R^ThreeAnd R^FourMay have a substituent
Alkyl group, aralkyl group which may have a substituent or
R represents an aryl group which may have a substituent; ¹,
R^Two, R^ThreeAnd R^FourAre the same but different
May be used; Ar¹And Ar^TwoIs an ant which may have a substituent
M, which may be the same or different;
Represents 0 or 1)(Where R^Five, R⁶, R⁹And R^TenMay have a substituent
Alkyl group, aralkyl group which may have a substituent or
An aryl group which may have a substituent;⁷And R⁸Is
Having an alkylene group or a substituent which may have a substituent
R represents an arylene group;^Five, R⁶, R⁹And R^TenWhen
R⁷And R⁸May be the same or different;
Q represents an organic residue which may have a substituent) 2. The compound according to claim 1, wherein in the general formula (1), the hole transporting compound in which the bonding site between A, P ¹ and Z is replaced by a hydrogen atom is represented by the general formula (2). Electrophotographic photoreceptor. 3. The compound according to claim 1, wherein in the general formula (1), the hole transporting compound in which the bonding site between A, P ¹ and Z is replaced by a hydrogen atom is represented by the general formula (3). Electrophotographic photoreceptor. 4. Z of general formula (1) or general formula (3)
Q is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ¹¹ ＣＲCR ¹² (where R ¹¹ and R ¹² are an alkyl group which may have a substituent, An aryl group or a hydrogen atom which may have a group, R ¹¹ and R ¹²
May be the same or different), C = O, S = O, S
O _2, electrophotographic photosensitive member according to claim 1, an organic residues combined in one or optionally more oxygen atom or a sulfur atom. 5. Z of the above general formula (1) or general formula (3)
Q is represented by the following general formula (4).
An electrophotographic photosensitive member according to any one of the above. Embedded image(Where X¹~ X^ThreeIs an alkylene which may have a substituent
Group, (CR¹³= CR¹⁴) M ¹, C = O, S = O, SO_Two,
Represents an oxygen atom or a sulfur atom;^ThreeAnd Ar^FourIs a substituent
R represents an arylene group optionally having¹³And R¹⁴Is
Alkyl group which may have a substituent, may have a substituent
R represents an aryl group or a hydrogen atom;¹³And R ¹⁴Are the same
May also be different; m¹Is an integer of 1 to 5, p to t is 0 or
Represents an integer of 1 to 10, provided that p to t are simultaneously 0
Never) 6. Z of the above general formula (1) or general formula (3)
5. The electrophotographic photosensitive member according to claim 1, wherein Q is represented by the following general formula (5). Embedded image (Wherein, Ar ⁵ represents an arylene group which may have a substituent; X ⁴ and X ⁵ represent (CH ₂ ) _g , (CH ＝ CR ¹⁵ ) _h ,
C = O or an oxygen atom; R ¹⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, g is an integer of 1 to 10, h is 1 Integers from 5 to 5, u to w each represent 0 or an integer from 1 to 10;
Are never 0 at the same time) 7. The method according to claim 1, wherein R ¹ and R ^{2 in} the general formula (2) are an aryl group which may have a substituent.
7. The electrophotographic photoreceptor according to any one of 6. 8. The electrophotographic photosensitive material according to claim 1, wherein R ^{1 to} R ^{4 in} the general formula (2) are an aryl group which may have a substituent. body. 9. At least two of R ⁵ , R ⁶ , R ⁹ and R ^{10 in} the general formula (3) are an aryl group which may have a substituent, and R ⁷ and R ⁸ are a substituent. 7. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is an arylene group which may have 10. R ⁵ , R ⁶ , R ⁹ and R ^{10 in the} general formula (3) are an aryl group which may have a substituent, and R ⁷ and R ^{8 each} have a substituent. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is an arylene group. 11. The electrophotographic photosensitive material according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² is an unsaturated polymerizable functional group represented by the following general formula (6). body. Embedded image (Wherein E is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, a cyano group, a nitro group, an alkoxy group, -COOR ¹⁶
{R ¹⁶ is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent} or -CONR ¹⁷ R
¹⁸ ｛R ¹⁷ and R ¹⁸ represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent, Represents the same or different｝, and W represents a divalent aryl group optionally having a substituent, a divalent alkylene group optionally having a substituent, -COO-, -O −, −
OO—, —S— or —CONR ¹⁹ — ｛R ¹⁹ is a hydrogen atom,
A halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent; f represents 0 or 1) 12. The electrophotographic photosensitive member according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² is a cyclic ether group represented by the following general formula (7). Embedded image (Wherein, R ²⁰ and R ²¹ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent, and n is 1 to 10
Indicates an integer) 13. The electrophotographic photoreceptor according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² is an alicyclic epoxy group represented by the following general formula (8). . Embedded image (Wherein, R ²² and R ²³ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent, and n is 0 or 1
Represents an integer from 10 to 10) 14. The electrophotographic photosensitive material according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² are any of the following formulas (9) to (15). body. Embedded image 15. The electrophotographic photosensitive member according to claim 14, wherein one or both of the chain polymerizable groups P ¹ and P ² are represented by the following general formula (9) or (10). Embedded image 16. The compound according to claim 1, wherein the oxidation potential of the hole transporting compound having two or more chain-polymerizable functional groups in the same molecule is 0.4 to 1.2 (V). An electrophotographic photoreceptor as described in Crab. 17. The electrophotographic photosensitive member according to claim 1, wherein the polymerization is performed by an electron beam. 18. The electrophotographic photosensitive member according to claim 17, wherein the acceleration voltage of the electron beam is 300 KV or less. 19. The electrophotographic photoreceptor according to claim 17, wherein the dose of the electron beam is 1 to 100 Mrad. 20. A charging means for charging the electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member on which an electrostatic latent image is formed is developed with toner. Developing means, and at least one means selected from the group consisting of a cleaning means for collecting residual toner on the electrophotographic photoreceptor after the transfer step, are integrally supported together, and are detachably attached to the electrophotographic apparatus main body. Characteristic process cartridge. 21. An electrophotographic photosensitive member according to claim 1, a charging means for charging said electrophotographic photosensitive member, and an exposure to said charged electrophotographic photosensitive member to form an electrostatic latent image. An electrophotographic apparatus comprising: an exposure unit; a developing unit that develops an electrophotographic photosensitive member having an electrostatic latent image formed thereon with toner; and a transfer unit that transfers a toner image on a transfer material.