JP2007055968A - Amine compound, electrophotographic photoreceptor having amine compound and process cartridge having the electrophotographic photoreceptor and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amine compound capable of providing high image quality photoreceptors which stably have high sensitivity even to the differences of various use environments and to the specification differences of loaded process cartridges and electrophotographic apparatuses, and to provide an electrophotographic photoreceptor having the compound. <P>SOLUTION: This amine compound is represented by the general formula. Therein, R<SB>1</SB>to R<SB>30</SB>are each independently H, substituted or non-substituted phenyl, a substituted or non-substituted alkyl, or a substituted or non-substituted alkoxy; one of R<SB>11</SB>to R<SB>30</SB>is substituted or non-substituted phenyl or a substituted or non-substituted alkyl; A is a bonding group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an amine compound, an electrophotographic photoreceptor using the amine compound, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus.

Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer mainly composed of selenium, zinc oxide, cadmium and the like has been widely used. Although these have some basic characteristics, there are problems such as difficulty in film formation, poor plasticity, and high manufacturing costs. Furthermore, inorganic photoconductive materials are generally highly toxic and have significant restrictions on manufacturing and handling.
On the other hand, an organic photoreceptor having a photosensitive layer mainly composed of an organic photoconductive compound has many advantages such as compensating for the above-mentioned drawbacks of inorganic photoreceptors, and has attracted attention in recent years. Has been put to practical use.

  Examples of such an organic photoreceptor include a charge transfer complex formed from a photoconductive polymer represented by poly-N-vinylcarbazole and a Lewis acid such as 2,4,7-trinitro-9-fluorenone. An electrophotographic photoreceptor having a photosensitive layer as a main component has been proposed. These organic photoconductive polymers are superior to inorganic photoconductive materials in terms of lightness, film formability, etc., but are inferior in terms of sensitivity, durability, stability due to environmental changes, etc. It is not satisfactory.

  However, the function-separated electrophotographic photosensitive member in which the charge generation function and the charge transport function are respectively assigned to different substances significantly improved the sensitivity and durability that were regarded as the disadvantages of the organic photosensitive member. Such a function-separated type photoconductor has the advantage that a wide range of materials can be selected for the charge generation material and the charge transport material, and an electrophotographic photoconductor having arbitrary characteristics can be produced relatively easily. .

  Further, it has been proposed to use a protective layer for the purpose of improving durability and transfer efficiency.

  As charge generation materials, various azo pigments, phthalocyanine pigments, polycyclic quinone pigments, cyanine dyes, squaric acid dyes, pyrylium salt dyes, and the like are known.

  Examples of the charge transport material include amine compounds such as pyrazoline compounds, hydrazone compounds, triphenylamine compounds (see Patent Documents 1 to 3), and stilbene compounds.

The requirements for these charge transport materials are: (1) stability to light and heat;
(2) Stable against ozone, NOx, nitric acid, etc. generated by corona discharge,
(3) having high charge injection efficiency;
(4) having a high charge transporting ability;
(5) being stable with respect to the production conditions of the protective layer;
(6) High compatibility with organic solvents and binders,
(7) It is easy to manufacture and inexpensive. However, conventional charge transport materials made of low molecular weight organic compounds satisfy some of the above-mentioned requirements, but none satisfy all of the above requirements, and there are many points to be improved.
JP-A-51-93224 JP-A-8-179526 JP 2003-146950 A

  It is an object of the present invention to provide an amine compound that satisfies the characteristics required for the above-described charge transport material, an electrophotographic photoreceptor using the amine compound, a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor. In other words, it has a stable and high sensitivity to the difference in various usage environments and the specifications of the process cartridge and the electrophotographic apparatus to be mounted. An object of the present invention is to provide a high-quality photoreceptor having excellent reproducibility. It is another object of the present invention to provide a novel amine compound that is easy to manufacture and inexpensive.

The amine compound according to the present invention is:
The following general formula (1)

（式中、Ｒ_１〜Ｒ_３０は、それぞれ独立に、水素原子、置換若しくは無置換のフェニル基、置換若しくは無置換のアルキル基、又は置換若しくは無置換のアルコキシ基を示し、但し、Ｒ_１１〜Ｒ_３０のうち一つは、置換若しくは無置換のフェニル基、又は置換若しくは無置換のアルキル基であることを示す。また、Ａは下記式

(Wherein R _{1 to} R ₃₀ each independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, provided that R ₁₁ to R 30 One of R ₃₀ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted alkyl group, and A represents the following formula:

又は

Or

を示し、Ｒ_３１は、水素原子又はアルキル基を示し、Ａｒは、置換又は無置換のフェニル基を示す。）
で示される化合物であることを特徴とする。

R ₃₁ represents a hydrogen atom or an alkyl group, and Ar represents a substituted or unsubstituted phenyl group. )
It is a compound shown by these.

In addition, according to the present invention, there is provided an amine compound represented by the following general formula (2) useful as an intermediate of the amine compound represented by the general formula (1):
The following general formula (2)

（式中、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５は、それぞれ独立に、水素原子、置換若しくは無置換のフェニル基、置換若しくは無置換のアルキル基、又は置換若しくは無置換のアルコキシ基を示し、但し、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５のうち一つは、置換若しくは無置換のフェニル基、又は置換若しくは無置換のアルキル基であることを示す。）
上記式（１）及び（２）のアルキル基としては、メチル基、エチル基、プロピル基等が挙げられる。また、式（１）及び（２）のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。

(Wherein R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ are each independently a hydrogen atom, a substituted or unsubstituted phenyl group, substituted or unsubstituted Represents a substituted alkyl group or a substituted or unsubstituted alkoxy group, provided that one of R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ is It indicates a substituted or unsubstituted phenyl group or a substituted or unsubstituted alkyl group.)
Examples of the alkyl group of the above formulas (1) and (2) include a methyl group, an ethyl group, and a propyl group. Moreover, as an alkoxy group of Formula (1) and (2), a methoxy group, an ethoxy group, a propoxy group etc. are mentioned.

  The electrophotographic photosensitive member according to the present invention is characterized in that in the electrophotographic photosensitive member having a photosensitive layer on a support, the photosensitive layer has the above-described amine compound.

Further, the process cartridge according to the present invention includes:
A process cartridge which is detachably attached to an electrophotographic apparatus main body, comprising the above-described electrophotographic photosensitive member, charging means for charging the surface of the electrophotographic photosensitive member, and an electrostatic formed on the electrophotographic photosensitive member. At least one means selected from the group consisting of developing means for developing a latent image with toner to form a toner image and cleaning means for removing toner remaining on the electrophotographic photoreceptor after the toner image is transferred; Are integrally supported.

Furthermore, the electrophotographic apparatus according to the present invention is:
The above-described electrophotographic photosensitive member, charging means for charging the surface of the electrophotographic photosensitive member, image exposing means for forming an electrostatic latent image on the charged electrophotographic photosensitive member by image exposure, and on the electrophotographic photosensitive member The image forming apparatus includes development means for developing the electrostatic latent image with toner to form a toner image, and transfer means for transferring the toner image on the electrophotographic photosensitive member to a transfer material.

  According to the amine compound of the present invention, production is easy and inexpensive, and an electrophotographic photoreceptor using the amine compound has high sensitivity and maintains a stable potential during repeated use. In addition, according to the process cartridge and the electrophotographic apparatus of the present invention, stable characteristics can be maintained against differences in use environment, specifications, and the like.

  The present invention is described in detail below.

  Typical specific examples of the amino compound represented by the general formula (1) are shown below. However, it is not limited to these compounds.

前記一般式（１）において、光、熱、及び帯電生成物に対して安定であり、また保護層の硬化条件による特性悪化を押さえることができる点で、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_９、及びＲ_１０が水素原子であり、且つＲ_３及びＲ_８がフェニル基であることが、好ましい。

In the general formula (1), R ₁ , R ₂ , R ₄ , R are stable in terms of light, heat, and charged product, and can suppress deterioration in characteristics due to the curing conditions of the protective layer. ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are preferably hydrogen atoms, and R ₃ and R ₈ are preferably phenyl groups.

Further, in the general formula (1), as described above, R ₁₁ , R and R are the same in that they are stable against light, heat, and a charged product, and can suppress deterioration in characteristics due to the curing conditions of the protective layer. Preferably, ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ , and R ₂₀ are hydrogen atoms, and R ₁₃ and R ₁₈ are phenyl groups.

Furthermore, in the general formula (1), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , It is particularly preferable that R ₁₆ , R ₁₇ , R ₁₉ , and R ₂₀ are hydrogen atoms, and R ₃ , R ₈ , R _13, and R ₁₈ are phenyl groups.

  Typical specific examples of the amino compound represented by the general formula (2) are shown below. However, it is not limited to these compounds.

一般式（２）で示されるアミン化合物は、ｍ−ジヨードベンゼンとジフェニルアミノ誘導体をＵｌｌｍａｎ反応することにより得ることができる。

The amine compound represented by the general formula (2) can be obtained by the Ullman reaction of m-diiodobenzene and a diphenylamino derivative.

  The amine compound represented by the general formula (1) can be obtained by Ullman reaction of the compound represented by the general formula (2) and the amine compound represented by the following general formula (3).

（式中、Ｒ_１〜Ｒ_１０、及びＡは上述に同じ）
本発明の電子写真感光体は、支持体上に、一般式（１）で示されるアミン化合物からなる電荷輸送材料と適当な電荷発生材料とを含有する感光層を有する。

(Wherein R _{1 to} R ₁₀ and A are the same as described above)
The electrophotographic photoreceptor of the present invention has a photosensitive layer containing a charge transport material composed of an amine compound represented by the general formula (1) and a suitable charge generation material on a support.

  As a structure of a photosensitive layer, the following form is mentioned from the side close | similar to a support body, for example.

(1) Layer containing charge generation material / Layer containing charge transport material (2) Layer containing charge transport material / Layer containing charge generation material (3) Layer containing charge generation material and charge transport material (4) Layer containing a charge generating material / Layer containing a charge generating material and a charge transporting material The amino compound represented by the general formula (1) has a high transport ability with respect to holes. Used as a charge transport material. When the photosensitive layer is in the form (1), negative charge is preferable, and in the case (2), positive charge is preferable. In the cases (3) and (4), either positive or negative charge can be used.

  Furthermore, the electrophotographic photosensitive member of the present invention may be provided with a protective layer or an insulating layer on the surface of the photosensitive layer in order to improve adhesion and control charge injection. The configuration of the electrophotographic photosensitive member of the present invention is not limited to the above basic configuration.

  Among the above basic configurations, the form (1) is particularly preferable and will be described in more detail. In the electrophotographic photosensitive member of the present invention, examples of the conductive support include the following forms.

(1) A metal or alloy such as aluminum, aluminum alloy, stainless steel, copper, etc., in the shape of a plate or drum,
(2) A thin film formed by depositing or laminating a metal such as aluminum, palladium, gold or platinum on a non-conductive support such as glass, resin or paper or the conductive support of (1),
(3) Deposit or coat a layer of a conductive compound such as a conductive polymer, tin oxide, indium oxide on a non-conductive support such as glass, resin, paper, or the conductive support described in (1) above. Formed by
Etc.

  Examples of effective charge generating materials used in the electrophotographic photosensitive member of the present invention include the following materials.

(1) azo pigments such as monoazo, bisazo and trisazo,
(2) phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine;
(3) Indigo pigments such as indigo and thioindigo,
(4) Perylene pigments such as perylene acid anhydride and perylene imide,
(5) Polycyclic quinone pigments such as anthraquinone and pyrenequinone,
(6) squarylium dye,
(7) pyrylium salt, thiopyrylium salt,
(8) a triphenylmethane dye,
(9) Inorganic materials such as selenium and amorphous silicon.
These charge generation materials may be used alone or in combination of two or more.

  The layer containing the charge generation material, that is, the charge generation layer can be formed by dispersing the charge generation material as described above in a suitable binder resin and coating it on a conductive support. . It can also be formed by forming a thin film on a conductive support by a dry method such as vapor deposition, sputtering, or CVD.

  The binder resin can be selected from a wide range of binder resins, such as polycarbonate, polyester, polyarylate, butyral resin, benzal resin, polystyrene, polyvinyl acetal, diallyl phthalate resin, acrylic resin, methacrylic resin, polyvinyl acetate. Phenol resin, silicone resin, polysulfone, styrene-butadiene copolymer, alkyd resin, epoxy resin, urea resin, vinyl chloride-vinyl acetate copolymer, and the like, but are not limited thereto. These resins may be used alone or in combination of two or more. The resin contained in the charge generation layer is 80% by mass or less, preferably 40% by mass or less. The charge generation layer preferably has a thickness of 5 μm or less, particularly 0.01 to 2 μm. Various sensitizers can also be added to the charge generation layer.

  The layer containing the charge transport material, that is, the charge transport layer can be formed by combining the amino compound represented by the general formula (1) and an appropriate binder resin. Examples of the binder resin used for forming the charge transport layer include the binder resin used in the charge generation layer, and further using a photoconductive polymer compound such as polyvinyl carbazole or polyvinyl anthracene. May be. The blending ratio of the binder resin to the amino compound represented by the general formula (1) is preferably 30 to 300 parts by mass of the amino compound per 100 parts by mass of the binder resin.

  The charge transport layer is electrically connected to the charge generation layer described above, and has a function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. Since the charge transport layer has a limit in transporting the charge carrier, the film thickness cannot be increased more than necessary, but a range of 5 to 40 μm, particularly 10 to 30 μm is preferable. Furthermore, an antioxidant, an ultraviolet absorber, a plasticizer, or a known charge transport material can be added to the charge transport layer as necessary.

  The charge transport layer can be formed by using an appropriate organic solvent and using a coating means such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, and a blade coating method.

  A protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer and improving durability.

  The protective layer is made of a suitable organic resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), polyamide, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, and styrene-acrylonitrile copolymer. It can be formed by dissolving with a solvent and coating on the photosensitive layer and drying, or by coating on the photosensitive layer and curing by heating, electron beam, ultraviolet rays or the like. The thickness of the protective layer is preferably 0.1 to 10 μm.

  Further, the protective layer may have lubricating particles such as conductive particles, an ultraviolet absorber, and fluorine atom-containing resin fine particles. As the conductive particles, metal oxide particles such as tin oxide and silica are preferable.

  The electrophotographic photoreceptor of the present invention can be used not only for electrophotographic copying machines but also widely in electrophotographic application fields such as laser printers, CRT printers, and electrophotographic plate making systems.

  Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.

  One embodiment of the electrophotographic apparatus of the present invention is shown in FIG.

  In FIG. 1, reference numeral 1 denotes a drum type electrophotographic photosensitive member of the present invention, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow about a shaft 1a. The electrophotographic photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on its peripheral surface by the charging means 2 during the rotation process, and then the exposure light L (laser) by the exposure means (not shown) in the exposure unit 3. Beam scanning exposure). As a result, electrostatic latent images corresponding to the exposure images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member. The electrostatic latent image is then developed as a toner image by the developing means 4, and the toner developed image is synchronized with the rotation of the electrophotographic photosensitive member 1 from the paper feeding unit (not shown). And the corona transfer means 5 sequentially transfer them onto the surface of the transfer material 9 fed between them. The transfer material 9 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, is introduced into the image fixing means 8, is subjected to image fixing, and is printed out as a copy (copy) outside the electrophotographic apparatus. The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by the removal of the transfer residual toner by the cleaning unit 6, is subjected to a charge removal process by the pre-exposure unit 7, and is repeatedly used for image formation. .

  Further, a process cartridge in which at least one means selected from the group consisting of a charging means, a developing means and a cleaning means is integrally supported with the photosensitive member and is detachable from the main body of the electrophotographic apparatus is also within the scope of the present invention. One embodiment of the process cartridge of the present invention is shown in FIG.

  The process cartridge shown in FIG. 2 has an electrophotographic photosensitive member 1, a charging unit 2, and a developing unit 4 in a container 20. This process cartridge is configured to be detachable from the electrophotographic apparatus main body by a guide means 12 such as a rail. The cleaning means 6 may optionally be arranged in the container 20.

  FIG. 3 shows another embodiment of the process cartridge and the electrophotographic apparatus of the present invention. As shown in FIG. 3, the process cartridge and the electrophotographic apparatus of the present invention use a direct charging member 10 as charging means, and contact the electrophotographic photosensitive member 1 with the direct charging member 10 to which voltage is applied. The body 1 may be charged (this charging method is hereinafter referred to as direct charging). In the apparatus of the present invention shown in FIG. 3, the toner image on the electrophotographic photosensitive member 1 is also directly transferred to the transfer material 9 by the charging member 23. That is, the toner image on the electrophotographic photosensitive member 1 is transferred to the transfer material 9 by bringing the direct charging member 23 to which voltage is applied into contact with the transfer material 9.

  Further, as shown in FIG. 4, the electrophotographic apparatus of the present invention accommodates at least the electrophotographic photosensitive member 1 and the direct charging member 10 in the first container 21 as the first process cartridge, and at least the developing means 4 is the first developing device 4. It is also possible to have a second process cartridge that is housed in two containers 22 and that these process cartridges are configured to be detachable from the main body of the electrophotographic apparatus. Further, the first process cartridge in FIG. 4 (the form in which at least the electrophotographic photosensitive member 1 and the direct charging member 10 are housed in the first container 21) is one form of the process cartridge of the present invention. The first process cartridge may optionally have the cleaning means 6 disposed in the container 21.

  When the electrophotographic apparatus is used as a copying machine or a printer, the exposure light L is controlled by scanning the laser beam, the light emitting diode array according to the reflected light or transmitted light from the original, or the signal obtained by converting the original into a read signal. This is done by driving or driving a liquid crystal shutter array.

  Hereinafter, examples of the present invention will be described in detail. However, the following examples do not limit the present invention, and the present invention is not limited to the examples. In the following examples, “part” means “part by mass”.

  In addition, IR (infrared spectroscopy) is measured by JASCO Corporation: FT / IR-420, NMR (nuclear magnetic resonance spectrum) is measured by JEOL Ltd .: EX-400, and mass spectrometry is BRUKER. Made by: REFLEX III-TOF (measurement mode: POSI) or by Shimadzu Corporation: QP-2000 (measurement mode: DI-MS).

<Synthesis of Exemplary Compound (D-1)>
(Synthesis Example 1)
After stirring 3 parts of di-p-tolylamine, 25 parts of m-diiodobenzene, 5 parts of copper powder and 3 parts of potassium carbonate in 100 parts of dichlorobenzene at 180 ° C. for 20 hours, the solid content is removed by filtration. did. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (the solvent was a mixed solvent of hexane: toluene = 10: 0 to 10: 1) to obtain 4 parts of exemplary compound (D-1).

  The mass spectrometry, IR and NMR data relating to the obtained exemplary compound (D-1) are shown below.

Mass spectrometry (DI-MS): m / Z = 399 (M ⁺ )
IR (cm ⁻¹ , KBr): 3023, 2915, 1579, 1507, 1469, 1322, 816, 766, 503
¹ H-NMR (400 MHz, CDCL3, 22 ° C.): δ = 7.32 (t, 1H, J = 2.0 Hz), 7.20 (dt, 1H, J = 7.6, 1.2 Hz), 7 .06 (d, 4H, J = 8.0 Hz), 6.96 (d, 4H, J = 8.0 Hz), 6.92 (ddd, 1H, J = 8.0, 2.0, 1.2 Hz) ), 6.86 (dd, 1H, J = 8.0, 7.6 Hz), 2.31 (s, 6H, CH3)
<Synthesis of Exemplary Compound (D-3)>
(Synthesis Example 2)
After stirring 10 parts of N- (p-tolyl) -4-biphenylamine, 90 parts of m-diiodobenzene, 13 parts of copper powder and 8 parts of potassium carbonate in 100 parts of dichlorobenzene at 180 ° C. for 10 hours. The solid was removed by filtration. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (the solvent was a mixed solvent of hexane: toluene = 10: 0 to 10: 2) to obtain 11 parts of exemplary compound (D-3).

  The mass spectrometry, IR, and NMR data relating to the obtained exemplary compound (D-3) are shown below.

Mass spectrometry (DI-MS): m / Z = 461 (M ⁺ )
IR (cm ⁻¹ , KBr): 3025, 1577, 1508, 1469, 1294, 989, 766, 519
¹ H-NMR (400 MHz, CDCL3, 27 ° C.): δ = 7.51 (d, 2H, J = 7.32 Hz), 7.42 (d, 2H, J = 8.54 Hz), 7.36 (m , 3H), 7.25 (m, 2H), 7.05 (m, 4H), 6.97 (d, 3H, J = 8.3 Hz), 6.87 (t, 1H) 2.29 (s) , 3H, CH3)
<Synthesis of Exemplary Compound (A-3)>
(Synthesis Example 3)
4.5 parts of the following compound,

合成例１で得た例示化合物（Ｄ−１）８．４部、銅粉３部及び炭酸カリウム４部を、ジクロロベンゼン５０部中で、１８０℃、３０時間加熱撹拌した後、固形分をろ過で除去した。減圧下溶媒を留去し、残渣をシリカゲルカラム（溶媒は、ヘキサン：トルエン＝４：１の混合溶媒）にて精製し、例示化合物の（Ａ−３）を４部得た。

8.4 parts of the exemplary compound (D-1) obtained in Synthesis Example 1, 3 parts of copper powder and 4 parts of potassium carbonate were heated and stirred in 50 parts of dichlorobenzene at 180 ° C. for 30 hours, and then the solid content was filtered. Removed. The solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (the solvent was a mixed solvent of hexane: toluene = 4: 1) to obtain 4 parts of (A-3) of the exemplified compound.

  The mass spectrometry, IR, and NMR data relating to the obtained exemplary compound (A-3) are shown below.

Mass spectrometry (TOF, POSI): m / Z = 1016 (M ⁺ )
IR (cm ⁻¹ , KBr): 3022, 2919, 2857, 1590, 1507, 1482, 1271, 814, 695, 504
¹ H-NMR (400 MHz, CDCL3, 26 ° C.): δ = 6.8-7.1 (m, 30H), 6.78 (dd, 4H, J = 8.3, 2.2 Hz), 6.53 (D, 4H, J = 7.8 Hz), 2.24 (s, 12H, CH3), 2.18 (s, 6H, CH3), 2.14 (brs, 10H, CH2), 1.52 (br , 6H, CH2)
<Synthesis of Exemplary Compound (B-2)>
(Synthesis Example 4)
5.7 parts of the following compound,

合成例１で得た例示化合物（Ｄ−１）８．８部、銅粉３部及び炭酸カリウム４部を、ジクロロベンゼン１５０部中で、１８０℃、３０時間加熱撹拌した後、固形分をろ過で除去した。減圧下溶媒を留去し、残渣をシリカゲルカラム（溶媒は、ヘキサン：トルエン＝５：１の混合溶媒）にて精製し、例示化合物（Ｂ−２）を８部得た。

8.8 parts of the exemplified compound (D-1) obtained in Synthesis Example 1, 3 parts of copper powder and 4 parts of potassium carbonate were heated and stirred at 150 ° C. for 30 hours in 150 parts of dichlorobenzene, and then the solid content was filtered. Removed. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (the solvent was a mixed solvent of hexane: toluene = 5: 1) to obtain 8 parts of exemplary compound (B-2).

  The data of mass spectrometry, IR and NMR concerning the exemplary compound (B-2) are shown below.

Mass spectrometry (TOF, POSI): m / Z = 1112 (M ⁺ )
IR (cm ⁻¹ , KBr): 3027, 2932, 2856, 1589, 1507, 1483, 1314, 1287, 815, 762, 695, 503
¹ H-NMR (400 MHz, CDCL3, 26 ° C.): δ = 7.52 (d, 4H, J = 7.6 Hz), 7.41 (d, 4H, J = 8.3 Hz), 7.38 (d , 4H, J = 8.8 Hz), 7.3-6.94 (m, 32H), 6.84 (s, 2H), 6.64 (d, 2H, J = 8.0 Hz), 6.60. (D, 2H, J = 8.0 Hz), 2.24 (s, 12H, CH3), 2.20 (br, 4H, CH2), 1.55 (br, 6H, CH2)
<Synthesis of Exemplary Compound (C-1)>
(Synthesis Example 5)
5.7 parts of the following compound,

合成例２で得た例示化合物（Ｄ−３）１０部、銅粉３部及び炭酸カリウム４部を、ジクロロベンゼン１００部中で、１８０℃、２０時間加熱撹拌した後、固形分をろ過で除去した。減圧下溶媒を留去し、残渣をシリカゲルカラム（溶媒は、ヘキサン：トルエン＝２：１の混合溶媒）にて精製し、例示化合物（Ｃ−１）を８部得た。

After 10 parts of the exemplified compound (D-3) obtained in Synthesis Example 2, 3 parts of copper powder and 4 parts of potassium carbonate were heated and stirred in 100 parts of dichlorobenzene at 180 ° C. for 20 hours, the solid content was removed by filtration. did. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (the solvent was a mixed solvent of hexane: toluene = 2: 1) to obtain 8 parts of exemplary compound (C-1).

  The mass spectrometry, IR, and NMR data concerning the exemplary compound (C-1) are shown below.

Mass spectrometry (TOF, POSI): m / Z = 1236 (M ⁺ )
IR (cm ⁻¹ , KBr): 3028, 2932, 2856, 1588, 1483, 1314, 1287, 832, 761, 695, 514
¹ H-NMR (400 MHz, CDCL3, 26 ° C.): δ = 7.5-6.9 (m, 54H), 6.90 (d, 2H, J = 1.47 Hz), 6.69 (t, 4H) ), 2.34 (s, 6H, CH3), 2.15 (brs, 4H, CH2), 1.50 (br, 6H, CH2)
Example 1
An aluminum cylinder having a diameter of 30 mm × 357.5 mm is used as a support, and a paint composed of the following materials is applied on the support by a dip coating method, dried at 140 ° C. for 30 minutes, and the film thickness is 18 μm. A fringe prevention layer was formed.

Conductive pigment: SnO ₂ coated barium sulfate 10 parts Resistance adjusting pigment: Titanium oxide 2 parts Binder resin: Phenol resin 6 parts Leveling material: Silicone oil 0.001 part Solvent: Methanol / methoxypropanol = 0.2 / 0. 8 15 parts Next, a solution obtained by dissolving 1 part of N-methoxymethylated nylon and 3 parts of copolymer nylon in a mixed solvent of 60 parts of methanol and 30 parts of n-butanol was applied thereto by a dip coating method. It was dried for 10 minutes at 0 ° C. to form an intermediate layer having a thickness of 0.7 μm.

  Next, 4 parts of hydroxygallium phthalocyanine having strong peaks at 7.4 ° and 28.2 ° with a Bragg angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction as a charge generation material, polyvinyl butyral (trade name: ESREC BX) -1, 2 parts by Sekisui Chemical Co., Ltd.) and 80 parts of cyclohexanone were dispersed for 6 hours in a sand mill using glass beads with a diameter of 0.8 mm, and then 70 parts of cyclohexanone and 150 parts of ethyl acetate were added to generate charge. A layer dispersion was prepared. This was applied by a dip coating method and dried at 80 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.17 μm.

  Next, 17 parts of Exemplified Compound (A-3) obtained in Synthesis Example (3) and 10 parts of polycarbonate resin (trade name: Iupilon Z-400, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) as a charge transport material were mixed with monochlorobenzene 90. Particulate and 20 parts of dichloromethane were dissolved in a mixed solvent to prepare a charge generation layer dispersion. This was applied by a dip coating method and dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 10 μm.

  Next, the following structural formula (4)

の硬化性モノマー化合物３２部、平均粒径０．２μｍのポリテトラフルオロエチレン粒子４部及び平均粒径０．１μｍ以下のポリテトラフルオロエチレン粒子４部を、ｎ−プロピルアルコール６０部に混合した後に分散処理を行い、表面保護層用塗料を調製した。この塗料を用いて、前記電荷輸送層上に保護層を塗布した後、窒素中において加速電圧８０ｋＶ、線量１．５Ｍｒａｄの条件で電子線を照射した後、同雰囲気下、１５０℃で５分間加熱処理を行った。このときの酸素濃度は２０ｐｐｍであった。さらに、感光体を大気中で１４０℃、１時間後乾燥させて、膜厚５μｍの保護層を形成し、電子写真感光体１を作製した。

After mixing 32 parts of the curable monomer compound, 4 parts of polytetrafluoroethylene particles having an average particle diameter of 0.2 μm and 4 parts of polytetrafluoroethylene particles having an average particle diameter of 0.1 μm or less with 60 parts of n-propyl alcohol. A dispersion treatment was performed to prepare a coating material for the surface protective layer. Using this paint, a protective layer was applied on the charge transport layer, then irradiated with an electron beam in nitrogen under conditions of an acceleration voltage of 80 kV and a dose of 1.5 Mrad, and then heated at 150 ° C. for 5 minutes in the same atmosphere. Processed. The oxygen concentration at this time was 20 ppm. Further, the photoconductor was dried in the air at 140 ° C. for 1 hour to form a protective layer having a thickness of 5 μm, and thus an electrophotographic photoconductor 1 was produced.

  The produced electrophotographic photosensitive member was changed to 23 ° C./55% using a blue laser remodeling machine of Canon Co., Ltd., copy machine GP-40 (the light source was changed to a 405 nm semiconductor laser and the pre-exposure was changed to a halogen lamp). N / N). The potential characteristics of the photosensitive member were measured by removing the developing unit from the copying machine main body and fixing the potential measuring probe at the developing position instead. At that time, the transfer unit was not in contact with the photoreceptor, and the paper was not passed.

  Under an N / N environment, the surface potential (Vd) is −700 V, the bright portion potential (VL) is −200 V, and the pre-exposure is performed so that the light amount is twice the halogen light amount that attenuates the surface potential of −700 V to −200 V. The charge setting, the image exposure amount, and the pre-exposure amount were adjusted. At that time, the necessary light amount (laser light amount necessary for light attenuation to -200 V when the dark portion potential was set to -700 V) and the residual potential (potential when a laser light amount three times the necessary light amount was irradiated) were measured. The results are shown in Table 8.

  Next, after leaving the photoreceptor together with an evaluation machine in an ultra-low humidity (N / L) environment of 23 ° C./5% RH for 3 days, under the same environment (N / L), the − The bright part potential was measured using the amount of light necessary for optical attenuation to 200V. Further, under the same environment (N / L), continuous 3,000 rotation VL endurance (entire black image mode) was performed, and the bright portion potential at the 3,000th rotation was measured. The results are shown in Table 9.

  Next, together with the same evaluation machine, after being left for 3 days in an environment of 30 ° C./80% RH (H / H), the light attenuated to 200 V in the N / N environment under the same environment (H / H). The bright part potential was measured using the amount of light necessary to achieve this. Further, under the same environment (H / H), VL durability (full-color black image mode) was performed continuously for 10,000 revolutions, and the bright part potential at 10,000 revolutions was measured. Further, the difference between the maximum value and the minimum value of the bright portion potential before endurance in the three environments (H / H environment, N / N environment, and N / L environment) was defined as the environment fluctuation potential. The results are shown in Table 10.

  A new electrophotographic photosensitive member produced in the same manner was used with Canon's copier GP-40 blue laser double speed remodeling machine (the light source was changed to a 405 nm semiconductor laser and the process speed was changed to double speed 420 mm / sec). The measurement was performed by removing the developing unit from the copying machine main body and fixing the potential measuring probe at the developing position instead. At that time, the transfer unit was not in contact with the photoreceptor, and the paper was not passed.

  Under an N / N environment, the surface potential (Vd) is −700 V, the bright portion potential (VL) is −200 V, and the pre-exposure is performed so that the light amount is twice the halogen light amount that attenuates the surface potential of −700 V to −200 V. The charge setting, the image exposure amount, and the pre-exposure amount were adjusted.

  Next, after leaving the photoreceptor together with an evaluation machine in an ultra-low humidity (N / L) environment of 23 ° C./5% RH for 3 days, under the same environment (N / L), the − The bright part potential was measured using the amount of light necessary for optical attenuation to 200V. Further, under the same environment (N / L), continuous 3,000 rotation VL endurance (entire black image mode) was performed, and the bright portion potential at the 3,000th rotation was measured. The results are shown in Table 11.

  Next, together with the same evaluation machine, after being left for 3 days in an environment of 30 ° C./80% RH (H / H), the light attenuated to 200 V in the N / N environment under the same environment (H / H). The bright part potential was measured using the amount of light necessary to achieve this. Further, under the same environment (H / H), VL durability (full-color black image mode) was performed continuously for 10,000 revolutions, and the bright part potential at 10,000 revolutions was measured. In addition, the difference between the maximum value and the minimum value of the bright portion potential before endurance in the three environments was defined as the environmental variation potential. The results are shown in Table 12.

(Example 2)
Except having replaced with exemplary compound (B-2) obtained by synthetic example (4) instead of exemplary compound (A-3) obtained by synthetic example (3) as a charge transport material in Example 1, implementation was carried out. An electrophotographic photoreceptor 2 was produced using the same method as in Example 1.

  The obtained electrophotographic photoreceptor 2 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Example 3)
Except having replaced with exemplary compound (C-1) obtained by the synthesis example (5) instead of the exemplary compound (A-3) obtained by the synthesis example (3) as a charge transport material in Example 1, implementation was carried out. An electrophotographic photoreceptor 3 was produced using the same method as in Example 1.

  The obtained electrophotographic photoreceptor 3 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

Example 4
In the same manner as in Example 1, an interference fringe preventing layer and an intermediate layer were formed on an aluminum cylinder.

  Next, as a charge generation material, the following structural formula (5)

のアゾ化合物１０部をシクロヘキサノン２００部と直径０．８ｍｍのガラスビーズ４７０部と共にサンドミル装置で６時間分散した後、同サンドミル装置に、ブチラール樹脂（商品名：エスレックＢＬ−Ｓ、積水化学工業（社）製）２部をシクロヘキサノン１８に溶解させたバインダー溶液を加えた。更に同サンドミルで２時間分散させ、シクロヘキサノン１００部と酢酸エチル２８０部を加えて電荷発生層用分散液を調製した。これを浸漬コーティング法で塗布し、８０℃で１０分間乾燥して、膜厚が０．１７μｍの電荷発生層を形成した。

10 parts of the azo compound was dispersed together with 200 parts of cyclohexanone and 470 parts of glass beads having a diameter of 0.8 mm in a sand mill device for 6 hours, and then the butyral resin (trade name: ESREC BL-S, Sekisui Chemical Co., Ltd.) )) A binder solution in which 2 parts were dissolved in cyclohexanone 18 was added. Further, the mixture was dispersed for 2 hours in the same sand mill, and 100 parts of cyclohexanone and 280 parts of ethyl acetate were added to prepare a charge generation layer dispersion. This was applied by a dip coating method and dried at 80 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.17 μm.

  Next, using the same method as in Example 1, a charge transport layer and a protective layer were formed to produce an electrophotographic photoreceptor 4.

  The obtained electrophotographic photoreceptor 4 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Example 5)
Implementation was performed except that instead of the exemplary compound (A-3) obtained in Synthesis Example (3) as the charge transport material in Example 4, the exemplary compound (B-2) obtained in Synthesis Example (4) was used instead of the exemplary compound (A-3). An electrophotographic photoreceptor 5 was produced using the same method as in Example 4.

  The obtained electrophotographic photoreceptor 5 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Example 6)
Except for replacing the exemplary compound (A-3) obtained in Synthesis Example (3) as the charge transport material in Example 4 with the exemplary compound (C-1) obtained in Synthesis Example (5), the procedure was carried out. An electrophotographic photoreceptor 6 was produced using the same method as in Example 4.

  The obtained electrophotographic photoreceptor 6 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Comparative Example 1)
The same method as in Example 1, except that the charge transporting material of the following structural formula (6) was used instead of the exemplified compound (A-3) obtained in Synthesis Example (3) as the charge transporting material in Example 1. Comparative photoreceptor 1 was prepared using

得た比較感光体１の評価を実施例１と同様に行った。評価結果を表８〜１２に示す。

The obtained comparative photoreceptor 1 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Comparative Example 2)
Instead of the exemplary compound (A-3) obtained in Synthesis Example (3) as the charge transport material in Example 1, instead of the charge transport material of the following structural formula (7), the same method as in Example 1 was used. Thus, the comparative photoreceptor 2 was prepared, but the solubility of the compound of the structural formula (7) was so poor that the charge transport layer coating material could not be prepared.

（比較例３）
実施例１において電荷輸送材料として合成例（３）で得られた例示化合物（Ａ−３）１７部の代わりに上記構造式（７）７部に代えた以外は、実施例１と同様の方法を用いて比較感光体３を作製した。

(Comparative Example 3)
The same method as in Example 1 except that instead of 17 parts of the exemplary compound (A-3) obtained in Synthesis Example (3) as a charge transport material in Example 1, the structural formula (7) was replaced with 7 parts. Comparative photoreceptor 3 was prepared using

  The obtained comparative photoreceptor 3 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Comparative Example 4)
The same method as in Example 1, except that the charge transporting material of the following structural formula (8) was used instead of the exemplified compound (A-3) obtained in Synthesis Example (3) as the charge transporting material in Example 1. Comparative photoreceptor 4 was prepared using

得た比較感光体４の評価を実施例１と同様に行った。評価結果を表８に示す。

The obtained comparative photoreceptor 4 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.

(Comparative Example 5)
The same method as in Example 1 except that in Example 1, instead of 17 parts of the exemplified compound (A-3) obtained in Synthesis Example (3) as a charge transport material, 7 parts of the above structural formula (8) was used. Comparative photoreceptor 5 was prepared using

  The obtained comparative photoreceptor 5 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Comparative Example 6)
A comparison was made using the same method as in Example 4 except that the structural formula (6) was used instead of the exemplified compound (A-3) obtained in Synthesis Example (3) as the charge transport material in Example 4. Photoconductor 6 was produced.

  The obtained comparative photoconductor 6 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Comparative Example 7)
In Example 4, the same method as in Example 4 except that instead of 17 parts of the exemplary compound (A-3) obtained in Synthesis Example (3) as the charge transport material, 7 parts of the structural formula (7) were used. Comparative photoreceptor 7 was prepared using

  The obtained comparative photoreceptor 7 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

(Comparative Example 8)
Example Compound (A-3) 1 obtained in Synthesis Example (3) as a charge transport material in Example 4
A comparative photoconductor 8 was prepared in the same manner as in Example 4 except that 7 parts in the structural formula (8) were used instead of 7 parts.

  The obtained comparative photoreceptor 8 was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 8-12.

注）３，０００回耐久後の変動値（Ｖ）の＋はＶＬアップを意味する。
例えば実施例の１の初期−２１０Ｖは耐久後、−２２８Ｖを意味する。

Note) + of fluctuation value (V) after 3,000 times of durability means VL up.
For example, the initial -210V in Example 1 means -228V after endurance.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including an electrophotographic photosensitive member of the present invention. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention. It is a figure which shows the example of schematic structure of another electrophotographic apparatus provided with the process cartridge which has the electrophotographic photoreceptor of this invention. FIG. 2 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a first process cartridge and a second process cartridge having the electrophotographic photosensitive member of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 1a Axis 2 Charging means 3 Exposure part 4 Developing means 5 Corona transfer means 6 Cleaning means 7 Pre-exposure means 8 Fixing means 9 Transfer material 10 Direct charging member 12 Guide means 20, 21, 22 Container 23 Direct charging member L Exposure light

Claims (8)

The following general formula (1)

(Wherein R _{1 to} R ₃₀ each independently represents a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, provided that R ₁₁ to R 30 One of R ₃₀ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted alkyl group, and A represents the following formula:

Or

R ₃₁ represents a hydrogen atom or an alkyl group, and Ar represents a substituted or unsubstituted phenyl group. )
An amine compound characterized by the following: In general formula (1),
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are hydrogen atoms;
The amine compound according to claim 1, wherein R ₃ and R ₈ are phenyl groups. In general formula (1),
R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ and R ₂₀ are hydrogen atoms;
The amine compound according to claim 1 or 2, wherein R ₁₃ and R ₁₈ are phenyl groups. The following general formula (2)

(Wherein R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ are each independently a hydrogen atom, a substituted or unsubstituted phenyl group, substituted or unsubstituted Represents a substituted alkyl group or a substituted or unsubstituted alkoxy group, provided that one of R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ is It indicates a substituted or unsubstituted phenyl group or a substituted or unsubstituted alkyl group.)
An amine compound characterized by the following: It is a manufacturing method of the amine compound according to claim 1,
A production method using the amine compound according to claim 4.   An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer includes the amine compound according to any one of claims 1 to 3.   A process cartridge which is detachably attached to an electrophotographic apparatus main body, comprising: the electrophotographic photosensitive member according to claim 6; charging means for charging a surface of the electrophotographic photosensitive member; and formed on the electrophotographic photosensitive member. At least selected from the group consisting of developing means for developing the electrostatic latent image formed with toner to form a toner image and cleaning means for removing toner remaining on the electrophotographic photosensitive member after the toner image is transferred A process cartridge which integrally supports one means.   7. The electrophotographic photosensitive member according to claim 6, a charging unit for charging the surface of the electrophotographic photosensitive member, an image exposure unit for forming an electrostatic latent image on the charged electrophotographic photosensitive member by image exposure, and electrophotography An electrophotographic apparatus comprising: a developing unit that develops an electrostatic latent image on a photoconductor with toner to form a toner image; and a transfer unit that transfers the toner image on the electrophotographic photoconductor to a transfer material. .

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