JP3907567B2 - Electrophotographic photosensitive member, process cartridge having the electrophotographic photosensitive member, and electrophotographic apparatus - Google Patents

Description

で示される電荷輸送材料７部と下記構造式
【００５５】
【化４】

で示される電荷輸送材料１部とポリアリレート樹脂１０部をモノクロルベンゼン７０部とメチラール３０部に溶解した溶液を調製し、電荷発生層上にディッピング法により塗布した。これを１１０℃の温度で１時間乾燥させて、膜厚が１８μｍの電荷輸送層を形成し電子写真感光体を作成した。
【００５６】
実施例１−２〜１−４および比較例１−１〜１−３
実施例１−１において用いたフタロシアニン結晶に代えて、表１に示したように製造例３−２、３−３、３−５、および３−４、３−６、３−７で製造したガリウムフタロシアニン結晶を用いた他は、実施例１−１と同様にして電子写真感光体をそれぞれ作成した。
【００５９】
実施例２−１
実施例１−１において用いたフタロシアニン結晶に代えて、製造例３−７で製造したガリウムフタロシアニン結晶を電荷発生材料として用い、ジメチルアミン硫酸塩をフタロシアニン化合物に対して４００ｐｐｍ添加した他は、実施例１−１と同様にして電子写真感光体を作成した。
【００６０】
比較例２−１
実施例１−１において用いたフタロシアニン結晶に代えて、製造例３−７で製造したガリウムフタロシアニン結晶を電荷発生材料として用い、下記構造式の電荷輸送材料（化合物Ｉ−１）をフタロシアニン化合物に対して４００ｐｐｍ添加した他は、実施例１−１と同様にして電子写真感光体を作成した。
【００６１】
【化５】

【００６２】
比較例２−２
実施例１−１において用いたフタロシアニン結晶に代えて、製造例３−７で製造したガリウムフタロシアニン結晶を電荷発生材料として用い、下記構造式のフェニレンジアミン誘導体（化合物Ｉ−２）をフタロシアニン化合物に対して１０％添加した他は、実施例１−１と同様にして電子写真感光体を作成した。
【００６３】
【化６】

【００６４】
比較例２−３
比較例２−２において用いた、前記フェニレンジアミン誘導体をフタロシアニン化合物に対して４００ｐｐｍ添加した他は、比較例２−２と同様にして電子写真感光体を作成した。
【００６５】
比較例２−４
比較例２−２において用いた、前記フェニレンジアミン誘導体をフタロシアニン化合物に対して４０ｐｐｍ添加した他は、比較例２−２と同様にして電子写真感光体を作成した。
【００６６】
比較例２−５
実施例１−１において用いたフタロシアニン結晶に代えて、製造例３−７で製造したガリウムフタロシアニン結晶を電荷発生材料として用い、ｔ−ブチルアミンをフタロシアニン化合物に対して４００ｐｐｍ添加した他は、実施例１−１と同様にして電子写真感光体を作成した。
【００６７】
実施例３−１
実施例１−４と同様に電荷発生層までを形成した。次に下記構造式
【００６８】
【化７】

で示される電荷輸送材料７部と下記構造式
【００６９】
【化８】

で示される電荷輸送材料３部、およびポリカーボネート樹脂（商品名：ユーピロンＺ−２００、三菱ガス化学社製）１０部をモノクロロベンゼン７０部に溶解した溶液を調製し、電荷発生層上にディッピング法により塗布した。これを１１０℃の温度で１時間乾燥させて、膜厚が２２μｍの電荷輸送層を形成し電子写真感光体を作成した。
【００７０】
比較例３−１
比較例１−１と同様に電荷発生層までを形成した。次に、実施例３−１と同様に電荷輸送層を形成し電子写真感光体を形成した。
【００７１】
比較例４−１
実施例１−１において用いたフタロシアニン結晶に代えて、下記構造式のアゾ化合物（化合物Ｉ−３）を電荷発生材料として用い、ジメチルアミンをアゾ化合物に対して４００ｐｐｍ添加した他は、実施例１−１と同様にして電子写真感光体を作成した。
【００７２】
【化９】

【００７３】
実施例１−１〜１−４、２−１、３−１、および比較例１−１〜１−３、２−１〜２−５、３−１、４−１で作成した電子写真感光体を以下の方法で評価した。
【００７４】
評価機はヒューレットパッカード社製ＬＢＰ「レーザージェット４０００」（プロセススピード９４．２ｍｍ／ｓｅｃ）を使用して、レーザー光を照射後の表面電位（明部電位）を測定した。表面電位は、評価機から、現像用カートリッジを抜き取り、そこに電位測定装置を挿入し測定を行った。電位測定装置は、現像用カートリッジの現像位置に電位測定プローブを配置することで構成されており、電子写真感光体に対する電位測定プローブの位置は、ドラム軸方向のほぼ中央、ドラム表面からのギャップを３ｍｍとした。測定は２５℃、相対湿度が５０％となる環境で行い、電子写真感光体ドラムは、測定の２４時間前から、測定環境に放置したものを用いた。
【００７５】
また、ポジゴーストの評価は以下のように行った。ベタ黒画像を２枚打ち出した後、プリント画像書き出しから感光体１回転の部分に２５ｍｍ角の正方形のベタ黒部を並べ、感光体２回転目以降に１ドットを桂馬パターンで印字したハーフトーンのテストチャートを打ち出し、ハーフトーンのテストチャート上に表れる、２５ｍｍ角のベタ黒部の履歴の程度を目視により評価した。ゴーストの程度は以下のようにランク基準に従い、数値化を行った。
ランクＡ：ゴーストは全く見えない。
ランクＢ：履歴の輪郭が極わずかに見える。
ランクＣ：履歴の輪郭がうっすら見える。
ランクＤ：履歴の輪郭がはっきりと見える。
ランクＥ：履歴の２５ｍｍ角がはっきりと見える。
【００７６】
評価結果を表１および表２に示す。
【００７７】
【表２】

【００７８】
【表３】

【００７９】
【発明の効果】
本発明は、高感度、特に半導体レーザー波長領域に高感度特性を有し、繰り返し使用時の電位安定性、加えて画像欠陥、特にゴーストの出にくい電子写真感光体が得られという顕著な効果を奏する電子写真感光体、該電子写真感光体を有するプロセスカートリッジおよび電子写真装置を可能にした。
【図面の簡単な説明】
【図１】本発明の電子写真感光体を有する電子写真装置の概略構成の例を示す図である。
【図２】本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成の例を示す図である。
【図３】本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成の例を示す図である。
【図４】本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成の例を示す図である。
【図５】製造例３−１で得られたヒドロキシガリウムフタロシアニンのＣｕＫαの特性Ｘ線回折図である。
【符号の説明】
１ 感光体
１ａ 軸
２ 帯電手段
３ 露光部
４ 現像手段
５ コロナ転写手段
６ クリーニング手段
７ 前露光手段
８ 定着手段
９ 転写材
１０ 直接帯電部材
１２ 案内手段
２０、２１、２２ 容器
２３ 直接帯電部材
Ｌ 露光光[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.
[0002]
[Prior art]
Inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been conventionally used as photoconductive materials for electrophotographic photoreceptors. On the other hand, organic photoconductive materials such as polyvinylcarbazole, oxadiazole, azo pigments, and phthalocyanines have advantages such as pollution-free and high productivity compared to inorganic photoconductive materials, but their sensitivity is low and their practical application is difficult. Met. For this reason, several sensitization methods have been proposed. As an effective method, use of a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated has become the mainstream and is put into practical use. It has become.
[0003]
On the other hand, in recent years, non-impact printers using electrophotographic technology have been widely used in place of conventional impact printers as terminal printers. These are mainly laser beam printers that use laser light as a light source. As the light source, a semiconductor laser is used from the viewpoint of cost, the size of the apparatus, etc., and electrophotographic photosensitive having sufficient sensitivity to light of the oscillation wavelength. The body has been developed.
[0004]
Phthalocyanine compounds are extremely effective as charge generation materials having sensitivity in such a semiconductor laser oscillation wavelength region, and in particular, oxotitanium phthalocyanine and gallium phthalocyanine have superior sensitivity characteristics compared to conventional phthalocyanine compounds. Have reported various crystal forms (for example, see Patent Documents 1 to 8).
[0005]
In addition, in the phthalocyanine compound, even when the crystal form is the same, when used as an electrophotographic photosensitive member due to a production method such as a raw material and a solvent, and a production condition such as a reaction temperature and a charging ratio, the electrophotographic characteristics are remarkably changed. In particular, it has been found that the sensitivity and chargeability are significantly different.
[0006]
Various methods for producing gallium phthalocyanine crystals have been disclosed (see, for example, Patent Documents 9 to 13). Further, hydroxygallium phthalocyanine crystals containing a polar organic solvent such as N, N-dimethylformamide have been disclosed (for example, see Patent Document 14). An electrophotographic photoreceptor using these gallium phthalocyanine crystals is Variations in the electrophotographic characteristics of each production occur, and are not always satisfactory from the viewpoint of increasing the speed of the electrophotographic process or improving the image quality.
[0007]
In addition, as an example of including an amine compound in a photoreceptor, it is a well-known fact that a tertiary amine compound is used as a charge transport material, and a primary or secondary amine compound is also disclosed (for example, Patent Document 15). However, these effects are improvement of sensitivity and durability potential fluctuation by improvement of hole transport capability, reduction of charging deterioration by antioxidation effect and improvement of wear of surface layer, from the viewpoint of high image quality. There is a demand for an electrophotographic photosensitive member that is not satisfactory, and that does not cause ghosting in further miniaturization of electrophotographic apparatuses such as copying machines and laser beam printers, and in high-quality full color.
[0008]
[Patent Document 1]
Japanese Patent Laid-Open No. 61-239248
[Patent Document 2]
JP-A-61-217050
[Patent Document 3]
JP-A 62-67094
[Patent Document 4]
Japanese Unexamined Patent Publication No. 63-218768
[Patent Document 5]
JP-A 64-17066
[Patent Document 6]
JP-A-5-098181
[Patent Document 7]
Japanese Patent Laid-Open No. 5-263007
[Patent Document 8]
JP 10-67946 A
[Patent Document 9]
JP-A-8-100134
[Patent Document 10]
JP-A-9-111148
[Patent Document 11]
JP-A-9-124967
[Patent Document 12]
Japanese Patent Laid-Open No. 10-7927
[Patent Document 13]
Japanese Patent Laid-Open No. 10-17784
[Patent Document 14]
JP 7-331107 A
[Patent Document 15]
JP 59-171741 A
[Patent Document 16]
JP-A-8-254844
[Patent Document 17]
JP-A-8-262760
[Patent Document 18]
JP 2000-122314 A
[0009]
[Problems to be solved by the invention]
The present invention has been made in view of these problems, and its object is to have high sensitivity, particularly high sensitivity characteristics in the semiconductor laser wavelength region, potential stability during repeated use, in addition to image defects, particularly ghosting. It is an object of the present invention to provide an electrophotographic photosensitive member which is difficult to obtain, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0010]
[Means for Solving the Problems]
  The present invention provides a charge generating material on a conductive support.galliumAn electrophotographic photoreceptor having a photosensitive layer comprising at least two layers of a charge generation layer containing a phthalocyanine compound and a charge transport layer containing a charge transport material, wherein the charge generation layer comprises:galliumFor phthalocyanine compoundsDimethylamine selected from dimethylamine and dimethylamine sulfate1 compound−An electrophotographic photoreceptor characterized by containing 500 ppm..
[0011]
  MaThe present invention is characterized in that the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported, and are detachable from the electrophotographic apparatus. Process cartridge.
[0012]
The present invention also provides an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a transfer unit.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0016]
  Used as a charge generation materialgalliumPhthalocyanine compounds are, PlaceCrystal form having strong peaks at 7.4 ± 0.3 ° and 28.2 ± 0.3 ° of Bragg angle 2θ in CuKα characteristic X-ray diffraction Of these, hydroxygallium phthalocyanine is preferred in terms of electrophotographic characteristics. Furthermore,Dimethylamine selected from dimethylamine and dimethylamine sulfateCompound contained in crystalgalliumPhthalocyanine crystals are particularly preferred because they exhibit excellent electrophotographic characteristics.
[0017]
  Dimethylamine selected from dimethylamine and dimethylamine sulfateCompoundgalliumThe content relative to the phthalocyanine compound is particularly preferably 5 to 200 ppm from the viewpoint of electrophotographic characteristics.
[0020]
Next, the electrophotographic photoreceptor of the present invention will be described in detail.
[0021]
The conductive support only needs to have conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, plastics, paper, and the like, and examples of the shape include a cylindrical shape or a film shape. It is done.
[0022]
An undercoat layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. As the material for the undercoat layer, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, gelatin and the like are used. These are dissolved in an appropriate solvent and coated on the conductive support. The film thickness is preferably 0.2 to 3.0 μm.
[0023]
Furthermore, it is preferable to provide a conductive layer between the support and the undercoat layer for the purpose of covering unevenness or defects on the support and preventing interference fringes. This can be formed by dispersing conductive powder such as carbon black, metal particles and metal oxide in a binder resin. The film thickness of the conductive layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.
[0024]
  The charge generation layer isgalliumWith phthalocyanine compoundsDimethylamine selected from dimethylamine and dimethylamine sulfateCompound, preferablyDimethylamine selected from dimethylamine and dimethylamine sulfateCompound contained in crystalgalliumPhthalocyanine compoundThingsDisperse in a suitable binder resin solution, apply this dispersion, and dry.
[0025]
The charge transport layer is formed by applying and drying a paint in which a charge transport material and a binder resin are mainly dissolved in a solvent. Examples of the charge transport material include various triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triallylmethane compounds.
[0026]
Examples of the binder resin used in each layer include resins such as polyester, acrylic resin, polyvinyl carbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinylidene chloride, acrylonitrile copolymer, and polyvinyl benzal. Used.
[0027]
As a method for applying the photosensitive layer, application methods such as a dipping method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, and a beam coating method can be used.
[0028]
  In the charge generation layergalliumThe content of the phthalocyanine compound is preferably 30 to 90% by mass, more preferably 50 to 80% by mass, based on the total solid content of the charge generation layer. The content of the charge transport material is preferably 20 to 80% by mass, more preferably 30 to 70% by mass with respect to the total solid content of the charge transport layer.
[0029]
A protective layer may be provided on the photosensitive layer as necessary. The protective layer is made of 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 dissolved by coating, coated on the photosensitive layer, and dried. The thickness of the protective layer is preferably 0.05 to 20 μm. Moreover, you may contain electroconductive particle, a ultraviolet absorber, etc. in a protective layer. As the conductive particles, metal oxides such as tin oxide particles are preferable.
[0030]
Next, an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention will be described.
[0031]
In FIG. 1, reference numeral 1 denotes a drum type photoconductor 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 photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the charging means 2 during the rotation process, and then the light image exposure L (slit exposure or laser exposure) is performed by the exposure means (not shown) in the exposure unit 3. Beam scanning exposure). As a result, electrostatic latent images corresponding to the exposure image are sequentially formed on the peripheral surface of the photosensitive member. The electrostatic latent image is then developed with toner by the developing unit 4, and the toner image is synchronized with the rotation of the photoconductor 1 between the photoconductor 1 and the transfer unit 5 from a paper feeding unit (not shown) by the corona transfer unit 5. It is sequentially transferred onto the surface of the transfer material 9 taken and fed. The transfer material 9 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the fixing means 8, and subjected to image fixing, and printed out as a copy (copy). After the image transfer, the surface of the photoreceptor 1 is cleaned by the transfer unit 6 after removal of the transfer residual toner, is subjected to a charge removal process by the pre-exposure unit 7 and repeatedly used for image formation.
[0032]
Further, in the apparatus shown in FIG. 2, at least the photosensitive member 1, the charging means 2 and the developing means 4 are accommodated in a container 20 to form a process cartridge, and this process cartridge is detachable using a guide means 12 such as a rail of the apparatus. It is composed. The cleaning means 6 may or may not be disposed in the container 20.
[0033]
Further, as shown in FIGS. 3 and 4, the photosensitive member 1 may be charged by using the direct charging member 10 as charging means and bringing the direct charging member 10 to which voltage is applied into contact with the photosensitive member 1 ( This charging method is hereinafter referred to as direct charging). In the apparatus shown in FIGS. 3 and 4, the toner image on the photoreceptor 1 is also directly transferred to the transfer material 9 by the charging member 23. That is, the direct charging member 23 to which voltage is applied is brought into contact with the transfer material 9 to transfer the toner image on the photoreceptor 1 to the transfer material 9.
[0034]
Further, in the apparatus shown in FIG. 4, at least the photosensitive member 1 and the direct charging member 10 are housed in a first container 21 to form a first process cartridge, and at least the developing means 4 is housed in a second container 22 to form a second container. The process cartridge is configured such that the first process cartridge and the second process cartridge are detachable. The cleaning means 6 may or may not be disposed in the container 21.
[0035]
When the electrophotographic apparatus is used as a copying machine or a printer, the optical image exposure L uses reflected light or transmitted light from a manuscript, or scans and emits a laser beam by this signal according to a signal read from the manuscript. This is performed by driving a diode array or a liquid crystal shutter array.
[0036]
Hereinafter, the present invention will be described in more detail in accordance with Production Examples, Examples, and Comparative Examples.
[0037]
“%” And “part” shown below mean “% by mass” and “part by mass”, respectively. α-Chloronaphthalene is manufactured by Tokyo Chemical Industry Co., Ltd. and has a purity of 85% or higher.
[0038]
Production Example 1-1
Under a nitrogen flow, 5.46 parts of phthalonitrile and 45 parts of α-chloronaphthalene were added to the reaction kettle and heated, and the temperature was raised to 60 ° C. to keep this temperature. At this point, the phthalonitrile was completely dissolved. Next, 3.75 parts of gallium trichloride was charged at this temperature (60 ° C.) (the water value of the reaction liquid at the time of charging was 83 ppm), and then the temperature was raised to 200 ° C. After reacting at 200 ° C. for 5.5 hours under a nitrogen flow, the product was filtered when cooled to 150 ° C. The obtained product was dispersed and washed at 140 ° C. for 2 hours with N, N-dimethylformamide, filtered, washed with methanol and dried to obtain 4.2 parts of chlorogallium phthalocyanine.
[0039]
Production Example 1-2
Under a nitrogen flow, 5.46 parts of phthalonitrile and 45 parts of α-chloronaphthalene were added to the reaction kettle and heated, and the temperature was raised to 60 ° C. to keep this temperature. At this point, the phthalonitrile was completely dissolved. Next, 3.75 parts of gallium trichloride was added at this temperature (60 ° C.) (the water content of the reaction liquid at the time of the addition was 30 ppm), and then the temperature was raised to 200 ° C. After reacting at 200 ° C. for 5.5 hours under a nitrogen flow, the product was filtered when cooled to 150 ° C. The obtained product was dispersed and washed with N, N-dimethylformamide at 140 ° C. for 2 hours, filtered, washed with methanol and dried to obtain 4.0 parts of chlorogallium phthalocyanine.
[0040]
Production Example 1-3
Under a nitrogen flow, 5.46 parts of phthalonitrile and 45 parts of α-chloronaphthalene were added to the reaction kettle and heated, and the temperature was raised to 30 ° C. to keep this temperature. At this point, phthalonitrile was not completely dissolved. Next, 3.75 parts of gallium trichloride was added at this temperature (30 ° C.) (the water content of the reaction liquid at the time of the addition was 20 ppm), and then the temperature was increased to 200 ° C. After reacting at 200 ° C. for 5.5 hours under a nitrogen flow, the product was filtered when cooled to 150 ° C. The obtained product was dispersed and washed with N, N-dimethylformamide at 140 ° C. for 2 hours, filtered, washed with methanol and dried to obtain 4.5 parts of chlorogallium phthalocyanine.
[0041]
Production Example 1-4
Under a nitrogen flow, 5.46 parts of phthalonitrile and 45 parts of α-chloronaphthalene were added to the reaction kettle and heated, and the temperature was raised to 30 ° C. to keep this temperature. At this point, phthalonitrile was not completely dissolved. Next, at this temperature (30 ° C.), 3.75 parts of gallium trichloride was added (the water value of the reaction liquid at the time of charging was 100 ppm), and then the temperature was raised to 200 ° C. After reacting at 200 ° C. for 3.5 hours under a nitrogen flow, the product was filtered when cooled to 150 ° C. The obtained product was dispersed and washed with N, N-dimethylformamide at 140 ° C. for 2 hours, filtered, washed with methanol and dried to obtain 4.3 parts of chlorogallium phthalocyanine.
[0042]
Production Example 2-1
2.25 parts of chlorogallium phthalocyanine obtained in Production Example 1-1 was dissolved in 67.5 parts of concentrated sulfuric acid at 5 to 10 ° C., dropped into 300 parts of ice water with stirring, and then reprecipitated, followed by filtration. . Dispersion washing with 2% aqueous ammonia, followed by dispersion washing with ion exchange water four times, followed by drying to obtain 2.1 parts of hydroxygallium phthalocyanine.
[0043]
Production Examples 2-2, 2-3, and 2-4
The chlorogallium phthalocyanine obtained in Production Examples 1-2, 1-3, and 1-4 was treated in the same manner as in Production Example 2-1.
[0044]
Production Example 3-1
Milling was performed at 25 ± 3 ° C. for 10 hours with 0.8 parts of hydroxygallium phthalocyanine obtained in Production Example 2-1 and 16 parts of N, N-dimethylformamide together with 24 parts of 1.2 mmφ glass beads. The solid content is taken out from this dispersion, sufficiently washed with tetrahydrofuran, and then vacuum-dried to obtain hydroxygallium phthalocyanine crystals having strong peaks at 7.5 ° and 28.3 ° of Bragg angle 2θ in CuKα characteristic X-ray diffraction. 0.7 parts were obtained. FIG. 5 shows a powder X-ray diffraction pattern of the obtained crystal. The crystals were wetted in methanol, then heat-treated with pure water and analyzed by ion chromatography to detect 400 ppm of dimethylamine.
[0045]
Production Examples 3-2, 3-3 and 3-4
In Production Examples 2-2, 2-3, and 2-4, the obtained hydroxygallium phthalocyanine was treated in the same manner as in Production Example 3-1. The powder X-ray diffraction of each of the crystals obtained was the same as in FIG. Analysis was conducted in the same manner as in Production Example 3-1, and dimethylamine was detected at 280 ppm, 360 ppm, and 660 ppm, respectively.
[0046]
Production Example 3-5
Milling was performed at 25 ± 3 ° C. for 10 hours with 0.8 parts of hydroxygallium phthalocyanine obtained in Production Example 2-1 and 16 parts of N, N-dimethylformamide together with 24 parts of 1.2 mmφ glass beads. The solid content is taken out from this dispersion, dispersed and washed with ion-exchanged water, and the subsequent filtration step is repeated three times to make completely wet from N, N-dimethylformamide wet, then freeze-dried, and CuKα characteristic X-ray 0.7 parts of a hydroxygallium phthalocyanine crystal having strong peaks at 7.5 ° and 28.3 ° with a Bragg angle 2θ of diffraction were obtained. The powder X-ray diffraction pattern of the obtained crystal was the same as in FIG. Analysis was conducted in the same manner as in Production Example 3-1, and 40 ppm of dimethylamine was detected.
[0047]
Production Example 3-6
Milling was performed at 25 ± 3 ° C. for 10 hours with 0.8 parts of hydroxygallium phthalocyanine obtained in Production Example 2-4 and 16 parts of N, N-dimethylformamide together with 24 parts of 1.2 mmφ glass beads. The solid content is taken out from this dispersion, dispersed and washed with ion-exchanged water, and the subsequent filtration step is repeated three times, followed by vacuum drying, and a Bragg angle 2θ of 7.5 ° and 28.28 in CuKα characteristic X-ray diffraction. 0.7 part of a hydroxygallium phthalocyanine crystal having a strong peak at 3 ° was obtained. The powder X-ray diffraction pattern of the obtained crystal was the same as in FIG. Analysis was conducted in the same manner as in Production Example 3-1, and 570 ppm of dimethylamine was detected.
[0048]
Production Example 3-7
Milling of the hydroxygallium phthalocyanine obtained in Production Example 2-1 and 16 parts of tetrahydrofuran together with 24 parts of 1.2 mmφ glass beads was carried out at 25 ° C. for 10 hours. The solid content was taken out from this dispersion and vacuum dried to obtain 0.7 parts of hydroxygallium phthalocyanine crystals having strong peaks at 7.5 ° and 28.3 ° of Bragg angle 2θ in CuKα characteristic X-ray diffraction. Analysis was conducted in the same manner as in Production Example 3-1, but dimethylamine was not detected.
[0049]
Example 1-1
50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resol type phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average A conductive layer coating material was prepared by dispersing 0.002 part of molecular weight 3000) in a sand mill apparatus using 1.2 mmφ glass beads for 2 hours.
[0050]
The paint was applied by dipping on an aluminum cylinder (φ30 mm) and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 16 μm.
[0051]
A solution prepared by dissolving 5 parts of 6-66-610-12 quaternary polyamide copolymer resin in a mixed solvent of 70 parts of methanol and 25 parts of butanol was applied by a dipping method and dried. A subbing layer of .5 μm was provided.
[0052]
Next, 2 parts of a hydroxygallium phthalocyanine crystal produced in Production Example 3-1 and 1 part of a polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 50 parts of cyclohexanone and a 1.2 mmφ glass. Disperse in a sand mill using beads for 6 hours, add 50 parts of cyclohexanone and 120 parts of ethyl acetate, dilute, apply this onto the undercoat layer, and dry at 100 ° C. for 10 minutes. A charge generation layer of 0.18 μm was formed.
[0053]
Next, the following structural formula (Compound I-1)
[0054]
[Chemical Formula 3]

7 parts of the charge transport material shown by the following structural formula
[0055]
[Formula 4]

A solution prepared by dissolving 1 part of the charge transport material and 10 parts of the polyarylate resin in 70 parts of monochlorobenzene and 30 parts of methylal was prepared and applied on the charge generation layer by dipping. This was dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a film thickness of 18 μm, thereby producing an electrophotographic photosensitive member.
[0056]
Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3
Instead of the phthalocyanine crystal used in Example 1-1, it was produced in Production Examples 3-2, 3-3, 3-5, and 3-4, 3-6, 3-7 as shown in Table 1. Except for using gallium phthalocyanine crystals, electrophotographic photoreceptors were prepared in the same manner as in Example 1-1.
[0059]
  Example 2-1
  Instead of the phthalocyanine crystal used in Example 1-1, the gallium phthalocyanine crystal produced in Production Example 3-7 was used as a charge generation material, and 400 ppm of dimethylamine sulfate was added to the phthalocyanine compound. An electrophotographic photoreceptor was prepared in the same manner as in 1-1.
[0060]
Comparative Example 2-1
Instead of the phthalocyanine crystal used in Example 1-1, the gallium phthalocyanine crystal produced in Production Example 3-7 was used as a charge generation material, and a charge transport material (compound I-1) having the following structural formula was used for the phthalocyanine compound. An electrophotographic photosensitive member was prepared in the same manner as in Example 1-1 except that 400 ppm was added.
[0061]
[Chemical formula 5]

[0062]
Comparative Example 2-2
Instead of the phthalocyanine crystal used in Example 1-1, the gallium phthalocyanine crystal produced in Production Example 3-7 was used as a charge generation material, and a phenylenediamine derivative (Compound I-2) having the following structural formula was used for the phthalocyanine compound. An electrophotographic photosensitive member was prepared in the same manner as in Example 1-1 except that 10% was added.
[0063]
[Chemical 6]

[0064]
Comparative Example 2-3
An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 2-2, except that 400 ppm of the phenylenediamine derivative used in Comparative Example 2-2 was added to the phthalocyanine compound.
[0065]
Comparative Example 2-4
An electrophotographic photoreceptor was prepared in the same manner as in Comparative Example 2-2, except that 40 ppm of the phenylenediamine derivative used in Comparative Example 2-2 was added to the phthalocyanine compound.
[0066]
Comparative Example 2-5
Example 1 except that the gallium phthalocyanine crystal produced in Production Example 3-7 was used as a charge generation material in place of the phthalocyanine crystal used in Example 1-1 and 400 ppm of t-butylamine was added to the phthalocyanine compound. An electrophotographic photoreceptor was prepared in the same manner as in Example-1.
[0067]
Example 3-1.
The layers up to the charge generation layer were formed as in Example 1-4. Next, the following structural formula
[0068]
[Chemical 7]

7 parts of the charge transport material shown by the following structural formula
[0069]
[Chemical 8]

A solution in which 3 parts of the charge transport material shown in FIG. 1 and 10 parts of polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Company) are dissolved in 70 parts of monochlorobenzene is prepared, and the solution is dipped on the charge generation layer. Applied. This was dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a film thickness of 22 μm, thereby producing an electrophotographic photosensitive member.
[0070]
Comparative Example 3-1
Similar to Comparative Example 1-1, the layers up to the charge generation layer were formed. Next, a charge transport layer was formed in the same manner as in Example 3-1, and an electrophotographic photosensitive member was formed.
[0071]
Comparative Example 4-1
In place of the phthalocyanine crystal used in Example 1-1, an azo compound (Compound I-3) having the following structural formula was used as a charge generation material, and 400 ppm of dimethylamine was added to the azo compound. An electrophotographic photoreceptor was prepared in the same manner as in Example-1.
[0072]
[Chemical 9]

[0073]
  Examples 1-1 to 1-4, 2-1,The electrophotographic photoreceptors prepared in 3-1, and Comparative Examples 1-1 to 1-3, 2-1 to 2-5, 3-1 and 4-1 were evaluated by the following methods.
[0074]
The evaluation machine used LBP “Laser Jet 4000” (process speed 94.2 mm / sec) manufactured by Hewlett-Packard Co., and measured the surface potential (light part potential) after irradiation with laser light. The surface potential was measured by removing the developing cartridge from the evaluation machine and inserting a potential measuring device there. The potential measuring device is configured by arranging a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe with respect to the electrophotographic photosensitive member is substantially at the center in the drum axis direction, with a gap from the drum surface. It was 3 mm. The measurement was performed in an environment where the temperature was 25 ° C. and the relative humidity was 50%, and the electrophotographic photosensitive drum was left in the measurement environment for 24 hours before the measurement.
[0075]
The positive ghost was evaluated as follows. After printing two solid black images, a halftone test was performed in which a solid black portion of 25 mm square was placed on the rotation of the photoconductor after the print image was written, and one dot was printed with a Keima pattern after the second rotation of the photoconductor. A chart was launched, and the degree of history of a solid black part of 25 mm square appearing on a halftone test chart was visually evaluated. The degree of ghost was quantified according to the rank criteria as follows.
Rank A: The ghost is not visible at all.
Rank B: The history outline is very slightly visible.
Rank C: The outline of the history is slightly visible.
Rank D: The outline of the history is clearly visible.
Rank E: The 25 mm square of the history is clearly visible.
[0076]
The evaluation results are shown in Tables 1 and 2.
[0077]
[Table 2]

[0078]
[Table 3]

[0079]
【The invention's effect】
The present invention has a remarkable effect that an electrophotographic photosensitive member having high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region, and potential stability during repeated use, in addition to image defects, in particular, ghosts are hardly generated. An electrophotographic photosensitive member, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member are made possible.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having an electrophotographic photosensitive member of the present invention.
FIG. 2 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
FIG. 3 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
FIG. 4 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
FIG. 5 is a characteristic X-ray diffraction pattern of CuKα of hydroxygallium phthalocyanine obtained in Production Example 3-1.
[Explanation of symbols]
1 Photoconductor
1a axis
2 Charging means
3 exposure part
4 Development 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 (7)

An electrophotographic photoreceptor having a photosensitive layer comprising at least two layers of a charge generation layer containing a gallium phthalocyanine compound as a charge generation material and a charge transport layer containing a charge transport material on a conductive support, wherein the charge generation layer comprises: dimethylamine compound selected from dimethylamine and dimethylamine sulphate 1 against phthalocyanine compound - 500 ppm electrophotographic photoreceptor, characterized in that it contains. The electrophotographic photosensitive member according to claim 1 , wherein the dimethylamine compound is dimethylamine . The electrophotographic photosensitive member according to claim 1 or 2 wherein the phthalocyanine compound is hydroxygallium phthalocyanine. It said dimethylamine compound 5 with respect to the charge generating material - 200 ppm electrophotographic photosensitive member according to any one of claims 1 to 3 containing. The phthalocyanine compound, an electrophotographic photosensitive member according to any one of claims 1 to 4 dimethylamine compound is gallium phthalocyanine compound contained in the crystal. 6. The electrophotographic photosensitive member according to claim 1, and at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit are integrally supported and detachable from the main body of the electrophotographic apparatus. A process cartridge characterized by that. The electrophotographic photosensitive member according to any one of claims 1 to 5, a charging means, image exposure means, the electrophotographic apparatus, characterized in that it comprises a developing means and transfer means.

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