JPH07140681A - Coating liquid for charge generating layer of electrophotographic photoreceptor and electrophotographic photoreceptor formed by using the same - Google Patents

Abstract

PURPOSE:To provide the coating liquid for the charge generating layer of the separated function electrophotographic photoreceptor which is prepd. by using a phthalocyanine compd. as a charge generating material and does not cause transition of a crystal type having a high sensitivity after an org. solvent treatment and to provide the production method of the electrophotographic photoreceptor used the same. CONSTITUTION:This coating liquid for the charge generating layer of the separated function electrophotographic photoreceptor having the charge generating layer on a conductive substrate and a charge transfer layer on the layer is prepd. by incorporating a water-soluble resin soln. to water paste of the phthalocyanine compd. This photoreceptor is formed by using such coating liquid. Since the coating liquid for the charge generating layer is produced without causing the transition of the crystal type having the high sensitivity, the separated function electrophotographic photoreceptor having the high sensitivity is produced.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は電子写真用感光体に係
り、特にレーザープリンターに好適な機能分離型電子写
真用感光体の電荷発生層用塗液及びそれを用いた機能分
離型電子写真用感光体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly to a coating liquid for a charge generation layer of a function-separated electrophotographic photoreceptor suitable for a laser printer, and a function-separated electrophotography using the same. Regarding the photoconductor.

【０００２】[0002]

【従来の技術】電子写真方式を用いた複写機及びレーザ
ープリンター用感光体として、電荷発生層と電荷輸送層
とから構成される機能分離型電子写真用感光体が実用化
されている。近年、これらの装置の光源には、信頼性の
観点から半導体レーザーが数多く用いられている。この
半導体レーザーの発振波長は、通常８００ｎｍ付近であ
るため長波長に高感度を有する電子写真用感光体の開発
が盛んに行われている。機能分離型電子写真用感光体の
感光波長領域は、電荷発生物質によって大きく左右され
る。特に長波長光に対して高感度を有する化合物とし
て、特開昭58−182639号公報に示されるτ型及びη型無
金属フタロシアニン、特開平3−128973号公報に示され
る各種結晶型のチタニルフタロシアニンが報告されてい
る。チタニルフタロシアニンの中で、ＣｕＫα特性Ｘ線
回折におけるブラッグ角（２θ±０.２度）が２７.２度
に最も強い回折ピークを有する結晶型が特に高感度を有
することが知られている。また、バナジルフタロシアニ
ンもＣｕＫα特性Ｘ線回折におけるブラッグ角（２θ±
０.２度）が２７.２度に最も強い回折ピークを有する結
晶型が特に高感度を有することが知られている。2. Description of the Related Art As a photoconductor for an electrophotographic copying machine or a laser printer, a function-separated type electrophotographic photoconductor composed of a charge generation layer and a charge transport layer has been put into practical use. In recent years, many semiconductor lasers have been used as the light source of these devices from the viewpoint of reliability. Since the oscillation wavelength of this semiconductor laser is usually around 800 nm, development of an electrophotographic photoreceptor having high sensitivity to long wavelengths has been actively conducted. The photosensitive wavelength region of the function-separated type electrophotographic photoconductor is greatly influenced by the charge generating substance. In particular, as compounds having high sensitivity to long-wavelength light, τ-type and η-type metal-free phthalocyanines disclosed in JP-A-58-182639 and various crystal-type titanyl phthalocyanines disclosed in JP-A-3-128973. Has been reported. It is known that among the titanyl phthalocyanines, the crystal form having the strongest diffraction peak at a Bragg angle (2θ ± 0.2 degrees) in CuKα characteristic X-ray diffraction of 27.2 degrees has particularly high sensitivity. In addition, vanadyl phthalocyanine also has a Bragg angle (2θ ± 2) in CuKα characteristic X-ray diffraction.
It is known that the crystal form having the strongest diffraction peak at 27.2 degrees (0.2 degrees) has particularly high sensitivity.

【０００３】高感度を有する結晶型のフタロシアニン化
合物の製造方法に関しては、特定の結晶型を有するフタ
ロシアニン化合物にミリングで機械的歪み力を与えて非
晶質あるいは低結晶性に変換させた後に、有機溶剤処理
によって目的の結晶型のフタロシアニン化合物を得る方
法が知られている。Regarding a method for producing a crystalline phthalocyanine compound having high sensitivity, a phthalocyanine compound having a specific crystalline type is mechanically strained by milling to convert it into an amorphous or low crystalline form, and then an organic compound is obtained. There is known a method of obtaining a desired crystalline phthalocyanine compound by solvent treatment.

【０００４】一方、特定の結晶型を有するフタロシアニ
ン化合物を硫酸に溶解し、この溶液を水中に滴下し再沈
せることで非晶質あるいは低結晶性に変換させた後、有
機溶剤処理によって高感度を有する結晶型を得る方法も
知られている。On the other hand, a phthalocyanine compound having a specific crystal form is dissolved in sulfuric acid, and the solution is dropped into water to be reprecipitated so as to be converted into an amorphous or low crystalline form, and then treated with an organic solvent to obtain high sensitivity. A method for obtaining a crystal form having is also known.

【０００５】この様にして得られた高感度を有するフタ
ロシアニン化合物は、電荷発生層に含まれる電荷発生材
料として使用される。ここで、電荷発生層を作製する方
法には、塗工が最も多く採用されている。したがって、
適宜選択された塗工方法に好適な電荷発生層用塗液が作
製され、使用されている。The highly sensitive phthalocyanine compound thus obtained is used as a charge generating material contained in the charge generating layer. Here, coating is most often used as the method for producing the charge generation layer. Therefore,
A charge generation layer coating liquid suitable for a coating method appropriately selected is prepared and used.

【０００６】[0006]

【発明が解決しようとする課題】該電荷発生層用塗液に
は塗工時の乾燥性，電荷発生材料の分散安定性，各種添
加剤（結着剤樹脂）との相溶性等から分散媒に有機溶剤
が使用されている。しかしながら、分散媒である有機溶
剤によって、高感度を有する結晶型のフタロシアニン化
合物は結晶転移を生じ、高感度が得られなくなるという
欠点があった。DISCLOSURE OF THE INVENTION The coating liquid for the charge generating layer has a dispersion medium because of its drying property during coating, dispersion stability of the charge generating material, compatibility with various additives (binder resin), and the like. An organic solvent is used in. However, there is a drawback in that the crystal type phthalocyanine compound having high sensitivity causes crystal transition due to the organic solvent as the dispersion medium, and high sensitivity cannot be obtained.

【０００７】本発明の目的は、このような欠点を除くた
めになされたもので、フタロシアニン化合物を電荷発生
材料とする電荷発生層用塗液において、結晶転移が生じ
ない高感度な電荷発生層用塗液及びそれを用いた電子写
真用感光体を提供することである。The object of the present invention is to eliminate such drawbacks, and in a charge generation layer coating liquid containing a phthalocyanine compound as a charge generation material, a highly sensitive charge generation layer for which no crystal transition occurs. A coating liquid and an electrophotographic photoreceptor using the same.

【０００８】[0008]

【課題を解決するための手段】本発明は、上記課題を解
決するためになされたもので、その要旨は次のとおりで
ある。The present invention has been made to solve the above problems, and its gist is as follows.

【０００９】本発明の第１の手段は、導電性支持体上に
電荷発生層、該層上に電荷輸送層を有する機能分離型電
子写真用感光体の電荷発生層用塗液において、該塗液が
フタロシアニン化合物の水ペーストに有機溶剤及び水溶
性樹脂溶液を配合してなることを特徴とする機能分離型
電子写真用感光体の電荷発生層用塗液。The first means of the present invention is a coating liquid for a charge generating layer of a function-separated electrophotographic photoreceptor having a charge generating layer on a conductive support and a charge transporting layer on the layer. A coating liquid for a charge generating layer of a function-separated type electrophotographic photoreceptor, which comprises a water paste of a phthalocyanine compound mixed with an organic solvent and a water-soluble resin solution.

【００１０】第２の手段は、導電性支持体上に電荷発生
層、該層上に電荷輸送層を有する機能分離型電子写真用
感光体の電荷発生層用塗液において、該塗液がチタニル
フタロシアニンの水ペーストに有機溶剤及び水溶性樹脂
溶液を配合してなり、該チタニルフタロシアニンがＣｕ
Ｋα特性Ｘ線回折においてブラッグ角（２θ±０.２
度）２７.２ 度に最大の回折ピークを有することを特徴
とする機能分離型電子写真用感光体の電荷発生層用塗
液。The second means is a coating liquid for a charge generation layer of a function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the conductive support, and the coating liquid is titanyl. An organic solvent and a water-soluble resin solution are mixed with an aqueous paste of phthalocyanine, and the titanyl phthalocyanine is Cu.
Bragg angle (2θ ± 0.2 in Kα characteristic X-ray diffraction
The coating liquid for the charge generation layer of the function-separated type electrophotographic photoconductor has a maximum diffraction peak at 27.2 degrees.

【００１１】第３の手段は、導電性支持体上に電荷発生
層、該層上に電荷輸送層を有する機能分離型電子写真用
感光体の電荷発生層用塗液において、該塗液がバナジル
フタロシアニンの水ペーストに有機溶剤及び水溶性樹脂
溶液を配合してなり、該バナジルフタロシアニンがＣｕ
Ｋα特性Ｘ線回折においてブラッグ角（２θ±０.２
度）２７.２ 度に最大の回折ピークを有することを特徴
とする機能分離型電子写真用感光体の電荷発生層用塗
液。A third means is a coating liquid for a charge generation layer of a function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, and the coating liquid is vanadyl. An organic solvent and a water-soluble resin solution are mixed with an aqueous paste of phthalocyanine, and the vanadyl phthalocyanine is Cu
Bragg angle (2θ ± 0.2 in Kα characteristic X-ray diffraction
The coating liquid for the charge generation layer of the function-separated type electrophotographic photoconductor has a maximum diffraction peak at 27.2 degrees.

【００１２】第４の手段は、前記有機溶剤がメチルエチ
ルケトンあるいはテトラヒドロフランであることを特徴
とする第２の手段及び第３の手段に記載の機能分離型電
子写真用感光体の電荷発生層用塗液。A fourth means is a coating liquid for a charge generating layer of a function-separated electrophotographic photoreceptor according to the second means and the third means, wherein the organic solvent is methyl ethyl ketone or tetrahydrofuran. .

【００１３】第５の手段は、前記水溶性樹脂が、セルロ
ース樹脂であることを特徴とする第２の手段及び第３の
手段に記載の機能分離型電子写真用感光体の電荷発生層
用塗液。In a fifth means, the water-soluble resin is a cellulose resin, and the coating for the charge generation layer of the function-separated electrophotographic photoreceptor is described in the second means and the third means. liquid.

【００１４】第６の手段は、導電性支持体上に電荷発生
層、該層上に電荷輸送層を有する機能分離型電子写真用
感光体の電荷発生層用塗液の製法において、該塗液がフ
タロシアニン化合物の水ペーストに有機溶剤及び水溶性
樹脂溶液を配合することを特徴とする機能分離型電子写
真用感光体の電荷発生層用塗液の製法。A sixth means is a method for producing a coating liquid for a charge generation layer of a function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer. Is a water-based paste of a phthalocyanine compound, and an organic solvent and a water-soluble resin solution are added to the charge-generating layer.

【００１５】第７の手段は、導電性支持体上に電荷発生
層、該層上に電荷輸送層を有する機能分離型電子写真用
感光体において、該電荷発生層の塗液がフタロシアニン
化合物の水ペーストに有機溶剤及び水溶性樹脂溶液を配
合してなることを特徴とする機能分離型電子写真用感光
体。The seventh means is a function-separated type electrophotographic photoreceptor having a charge generating layer on a conductive support and a charge transporting layer on the conductive support, and the coating liquid for the charge generating layer is water containing a phthalocyanine compound. A function-separated type electrophotographic photoreceptor comprising a paste and an organic solvent and a water-soluble resin solution.

【００１６】第８の手段は、導電性支持体上に電荷発生
層、該層上に電荷輸送層を有する機能分離型電子写真用
感光体において、該電荷発生層の塗液がチタニルフタロ
シアニンの水ペーストに有機溶剤及び水溶性樹脂溶液を
配合してなり、該チタニルフタロシアニンがＣｕＫα特
性Ｘ線回折においてブラッグ角（２θ±０.２ 度）２
７.２ 度に最大の回折ピークを有することを特徴とする
機能分離型電子写真用感光体。The eighth means is a function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, and the coating liquid for the charge generation layer is water of titanyl phthalocyanine. The paste contains an organic solvent and a water-soluble resin solution, and the titanyl phthalocyanine has a Bragg angle (2θ ± 0.2 degrees) of 2 in CuKα characteristic X-ray diffraction.
A function-separated type electrophotographic photosensitive member having a maximum diffraction peak at 7.2 degrees.

【００１７】第９の手段は、導電性支持体上に電荷発生
層、該層上に電荷輸送層を有する機能分離型電子写真用
感光体において、該電荷発生層の塗液がバナジルフタロ
シアニンの水ペーストに有機溶剤及び水溶性樹脂溶液を
配合してなり、該バナジルフタロシアニンがＣｕＫα特
性Ｘ線回折においてブラッグ角（２θ±０.２ 度）２
７.２ 度に最大の回折ピークを有することを特徴とする
機能分離型電子写真用感光体。A ninth means is a function-separated type electrophotographic photoreceptor having a charge generating layer on a conductive support and a charge transporting layer on the layer, and the coating liquid for the charge generating layer is water of vanadyl phthalocyanine. The paste contains an organic solvent and a water-soluble resin solution, and the vanadyl phthalocyanine has a Bragg angle (2θ ± 0.2 degrees) of 2 in CuKα characteristic X-ray diffraction.
A function-separated type electrophotographic photosensitive member having a maximum diffraction peak at 7.2 degrees.

【００１８】第１０の手段は、前記有機溶剤がメチルエ
チルケトンあるいはテトラヒドロフランであることを特
徴とする第８の手段及び第９の手段に記載の機能分離型
電子写真用感光体。The tenth means is a function-separated type electrophotographic photoreceptor as described in the eighth means and the ninth means, wherein the organic solvent is methyl ethyl ketone or tetrahydrofuran.

【００１９】第１１の手段は、前記水溶性樹脂が、セル
ロース樹脂であることを特徴とする第８の手段及び第９
の手段に記載の機能分離型電子写真用感光体。The eleventh means is the eighth means and the ninth means characterized in that the water-soluble resin is a cellulose resin.
The function-separated type electrophotographic photoconductor described in 1.

【００２０】本発明においてフタロシアニン化合物と
は、無金属フタロシアニン，銅フタロシアニン，アルミ
クロロフタロシアニン，クロロインジウムフタロシアニ
ン，マグネシウムフタロシアニン，亜鉛フタロシアニ
ン，チタニルフタロシアニン，バナジルフタロシアニン
等がある。この中で、チタニルフタロシアニン及びバナ
ジルフタロシアニンが電子写真特性上好ましい。In the present invention, the phthalocyanine compound includes metal-free phthalocyanine, copper phthalocyanine, aluminum chlorophthalocyanine, chloroindium phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, titanyl phthalocyanine, vanadyl phthalocyanine and the like. Among these, titanyl phthalocyanine and vanadyl phthalocyanine are preferable in terms of electrophotographic characteristics.

【００２１】本発明において、水ペーストにおけるフタ
ロシアニン化合物は、特定の結晶型を有さない非晶質あ
るいは低結晶性が好ましい。通常、この様な水ペースト
を作製するには、ミリングによって得られた非晶質ない
し低結晶性のフタロシアニン化合物に水を添加する方法
もあるが、アシッドペースティング法（硫酸に溶解後、
水に再沈させる方法）によって得られる水ペーストの方
が比較的分散安定性に優れ、塗液調合上好ましい。アシ
ッドペースティング法においても用いる硫酸の量，水の
量，処理温度等の条件により種々の低結晶性ないし非晶
質となるが、これら結晶型は混合物であっても構わな
い。In the present invention, the phthalocyanine compound in the water paste is preferably amorphous or low crystalline, which does not have a specific crystal type. Usually, in order to prepare such a water paste, there is a method of adding water to an amorphous or low crystalline phthalocyanine compound obtained by milling, but an acid pasting method (after dissolving in sulfuric acid,
The water paste obtained by the method of reprecipitation in water) is relatively excellent in dispersion stability and is preferable in coating liquid preparation. Also in the acid pasting method, various low crystalline or amorphous forms depending on the conditions such as the amount of sulfuric acid used, the amount of water used, the treatment temperature, etc., but these crystal forms may be a mixture.

【００２２】本発明において有機溶剤とは、アルコール
類，ケトン類，エステル類及びエーテル類等があり、こ
の中でブラッグ角（２θ±０.２度）２７.２度に最大の
回折ピークを有することを特徴とするチタニルフタロシ
アニンでは、メチルエチルケトン及びテトラヒドロフラ
ンが好ましいことが実験的に知られている。In the present invention, the organic solvent includes alcohols, ketones, esters, ethers, etc., and has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees. It is experimentally known that methylethylketone and tetrahydrofuran are preferable for the titanyl phthalocyanine characterized by the above.

【００２３】本発明において水溶性樹脂とは、分子中に
極性基を有し、水に溶解するポリマーであり、具体的に
はポリビニルアルコール樹脂，ポリアクリル酸樹脂，セ
ルロース樹脂，ポリアクリルアミド樹脂，ポリエチレン
オキシド樹脂，ポリエチレンイミン樹脂，ポリビニルピ
ロリドン樹脂等がある。In the present invention, the water-soluble resin is a polymer having a polar group in the molecule and soluble in water, and specifically, polyvinyl alcohol resin, polyacrylic acid resin, cellulose resin, polyacrylamide resin, poly Examples include ethylene oxide resin, polyethyleneimine resin, and polyvinylpyrrolidone resin.

【００２４】実際の塗液作製方法としては、予め秤量し
たフタロシアニン化合物の水ペーストに、有機溶剤及び
水溶性樹脂溶液を添加する。その後、既知のミリング装
置、例えばボールミル，ペイントシェーカー，サンドグ
ラインドミル，ロールミル，アトライター，振とう機及
び超音波洗浄機等の分散機を用いて十分分散処理する。
このようにしてできた塗液を既知の塗工法、例えばバー
コータ，ロールコータ，アプリケータ，スピンナー，流
延法及び浸漬法等により、電荷発生層が作製される。As an actual method of preparing a coating liquid, an organic solvent and a water-soluble resin solution are added to a water paste of a phthalocyanine compound which is weighed in advance. After that, a well-known milling device such as a ball mill, a paint shaker, a sand grind mill, a roll mill, an attritor, a shaker, and an ultrasonic cleaner is used to perform sufficient dispersion treatment.
The charge generation layer is produced by a known coating method such as a bar coater, a roll coater, an applicator, a spinner, a casting method and a dipping method.

【００２５】[0025]

【作用】本発明の塗料液の製法により、高感度を有する
結晶型への転移と電荷発生用塗液の調合が同時に行わ
れ、本発明の塗液が作製される。本発明の塗液の製法
は、結晶転移のため高感度が得られなくなるという従来
の欠点を克服するものである。According to the method for producing the coating liquid of the present invention, the transfer to the crystal form having high sensitivity and the preparation of the charge generating coating liquid are simultaneously carried out to prepare the coating liquid of the present invention. The method for producing the coating liquid of the present invention overcomes the conventional drawback that high sensitivity cannot be obtained due to crystal transition.

【００２６】非晶質状態からの結晶転移においては、水
の存在下における有機溶剤処理の中で長時間２７.２ 度
に最も強い回折ピークを有していることから、水の存在
が結晶型の維持に大きく関与していることが考えられ
る。In the crystal transition from the amorphous state, the presence of water is the crystalline form because it has the strongest diffraction peak at 27.2 degrees for a long time in the organic solvent treatment in the presence of water. It is thought that it is greatly involved in the maintenance of.

【００２７】したがって、本発明は親水性の溶剤で目的
の結晶型に転移し、かつ水の存在下により転移した結晶
型と結着剤樹脂の溶解性を安定に維持することができ、
高感度を有する電荷発生層用塗液が得られたものと考察
する。Therefore, according to the present invention, it is possible to stably maintain the solubility of the crystal form and the binder resin which have been transformed to the desired crystal form in the presence of water and which have been transformed in the presence of water.
It is considered that the coating liquid for the charge generation layer having high sensitivity was obtained.

【００２８】[0028]

【実施例】本発明を実施例により具体的に説明する。EXAMPLES The present invention will be specifically described with reference to examples.

【００２９】〔合成例〕フタロジニトリル６５重量部と
五酸化チタニウム２５重量部をα−クロロナフタレン５
００重量部に添加し、２００℃で３時間攪拌して反応さ
せた。反応終了後、熱時瀘過を行いα−クロロナフタレ
ンで洗浄した。次いで、アセトンで洗浄し、チタニルフ
タロシアニンを得た。[Synthesis Example] 65 parts by weight of phthalodinitrile and 25 parts by weight of titanium pentoxide were mixed with 5 parts of α-chloronaphthalene 5
It was added to 00 parts by weight and reacted at 200 ° C. for 3 hours with stirring. After completion of the reaction, the mixture was filtered while hot and washed with α-chloronaphthalene. Then, it was washed with acetone to obtain titanyl phthalocyanine.

【００３０】〔実施例１〕合成例で得たチタニルフタロ
シアニン１０重量部を濃硫酸１００重量部に溶解させ
た。次に氷水２５００重量部に、この硫酸溶液を２重量
部／分の速度で滴下して再析出させ、遠心分離機を用い
て、上澄み液の除去及び水の添加を数回繰り返しによる
洗浄を行い、チタニルフタロシアニンの水ペーストを得
た。Example 1 10 parts by weight of the titanyl phthalocyanine obtained in the synthesis example was dissolved in 100 parts by weight of concentrated sulfuric acid. Next, the sulfuric acid solution was added dropwise to 2500 parts by weight of ice water at a rate of 2 parts by weight / minute to reprecipitate, and the supernatant was removed and water was added several times using a centrifuge to perform washing. An aqueous paste of titanyl phthalocyanine was obtained.

【００３１】次に、この水ペースト２重量部（固形分濃
度：５０ｗｔ％）に、ヒドロキシプロピルメチルセルロ
ース（信越化学工業製，メトローズ６０ＳＨ５０）１重
量部を水４７重量部及びテトラヒドロフラン５０重量部
に溶解させた溶液を添加し、振とう機で２時間の攪拌を
行った後、さらに２時間の超音波分散処理を行って、電
荷発生層用塗液を得た。この塗液をスピンコート装置
（三笠セミコンダクター製，ミカサスピンナー１Ｈ２
型）を用い、導電性支持体として厚さ１００μｍのアル
ミニウム板上に塗工，乾燥（１２０℃，１時間）して、
電荷発生層を形成した。Next, 1 part by weight of hydroxypropylmethyl cellulose (Metronose 60SH50 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 2 parts by weight of this water paste (solid content concentration: 50 wt%) in 47 parts by weight of water and 50 parts by weight of tetrahydrofuran. The resulting solution was added, and the mixture was stirred for 2 hours with a shaker, and then subjected to ultrasonic dispersion treatment for 2 hours to obtain a charge generation layer coating liquid. This coating solution is applied to a spin coater (Mikasa Spinner 1H2, manufactured by Mikasa Semiconductor).
Mold), and is applied as a conductive support on an aluminum plate having a thickness of 100 μm and dried (120 ° C., 1 hour),
A charge generation layer was formed.

【００３２】次に、ポリカーボネート樹脂（帝人化成
製，パンライトＬ−１２５０）７重量部を塩化メチレン
４５重量部及びトルエン４５重量部に溶解させた。この
溶液に電荷輸送物質として下式（化１）に示すトリフェ
ニルアミン化合物（日本感光色素研究所製，ＮＫＸ−１
２０３）３重量部及びレベリング材（信越化学工業製，
ＫＰ−３２３）０.０１ 重量部を加えて溶解し、電荷輸
送層用塗液を得た。Next, 7 parts by weight of a polycarbonate resin (manufactured by Teijin Chemicals, Panlite L-1250) was dissolved in 45 parts by weight of methylene chloride and 45 parts by weight of toluene. A triphenylamine compound represented by the following formula (Chemical formula 1) as a charge transporting substance in this solution (NKX-1 manufactured by Japan Photosensitive Dye Research Institute)
203) 3 parts by weight and leveling material (manufactured by Shin-Etsu Chemical Co., Ltd.,
KP-323) 0.01 part by weight was added and dissolved to obtain a coating liquid for charge transport layer.

【００３３】[0033]

【化１】 [Chemical 1]

【００３４】この塗液を浸漬法により電荷発生層上に塗
工，乾燥（１２０℃，１時間）して電荷輸送層（厚さ：
１５μｍ）を形成し、電子写真用の機能分離型感光体を
得た。This coating solution is applied onto the charge generation layer by a dipping method and dried (120 ° C., 1 hour) to form a charge transport layer (thickness:
15 μm) was formed to obtain a function-separated photoreceptor for electrophotography.

【００３５】上記の感光体について、静電記録紙評価装
置（川口電機製，ＳＰ−４２８型）を用い、電子写真特
性を測定した。測定は、−５ＫＶのコロナ帯電を１０秒
間行い、この時の帯電電位Ｖ₀(−Ｖ）、次いで暗所に１
０秒間放置した時の帯電電位Ｖ₁₀（−Ｖ）を測定し、暗
減衰Ｖ₁₀／Ｖ₀(％）を求めた。感度は暗所に１０秒間放
置後、照度２ｌｘの白色光で露光し、露光前の電位が半
分になるまでに要する時間を求め、この時間と照度の積
（ｌｘ・ｓ）で求めた。The electrophotographic characteristics of the above-mentioned photoconductors were measured by using an electrostatic recording paper evaluation device (Kawaguchi Denki, SP-428 type). The measurement was carried out by corona charging at -5 KV for 10 seconds, charging potential V ₀ (-V) at this time, then 1 in the dark.
The charging potential V ₁₀ (−V) when left for 0 seconds was measured, and the dark decay V ₁₀ / V ₀ (%) was obtained. The sensitivity was left for 10 seconds in a dark place, exposed with white light having an illuminance of 2 lx, and the time required for the potential before exposure to be halved was determined, and the product was calculated by the product of this time and the illuminance (lx · s).

【００３６】本実施例の電子写真用感光体は、帯電電位
−９７０Ｖ，暗減衰８０％，感度０.５ｌｘ・ｓ と高感
度であった。The electrophotographic photosensitive member of this example had a high charging sensitivity of −970 V, dark decay of 80%, and sensitivity of 0.5 lx · s.

【００３７】塗液での結晶型を確認するため、上記チタ
ニルフタロシアニンの水ペースト２重量部に、水４７重
量部及びテトラヒドロフラン５０重量部の混合液を添加
し、塗液作製時と同様な分散処理を行った。その後乾燥
して、ＣｕＫα特性Ｘ線回折を測定した。結果を図１に
示すが、２７.２ 度に最も強い回折ピークを有してい
た。In order to confirm the crystal form of the coating liquid, a mixed solution of 47 parts by weight of water and 50 parts by weight of tetrahydrofuran was added to 2 parts by weight of the above-mentioned water paste of titanyl phthalocyanine, and the same dispersion treatment as in the preparation of the coating liquid was performed. I went. Then, it was dried and the CuKα characteristic X-ray diffraction was measured. The results are shown in FIG. 1, which had the strongest diffraction peak at 27.2 degrees.

【００３８】〔比較例〕実施例１のチタニルフタロシア
ニン水ペースト２重量部（固形分濃度：５０ｗｔ％）
に、水４７重量部及びテトラヒドロフラン５０重量部の
混合溶液を添加し、振とう機で２時間攪拌した。その
後、遠心分離機で上澄み液と沈殿物に分離して上澄み液
を除去し、沈殿物を減圧乾燥して、チタニルフタロシア
ニンを得た。この化合物のＣｕＫα特性Ｘ線回折図は図
１に示す様に、２７.２ 度に最大の回折ピークを示すも
のであった。Comparative Example 2 parts by weight of the titanyl phthalocyanine water paste of Example 1 (solid content concentration: 50 wt%)
To this, a mixed solution of 47 parts by weight of water and 50 parts by weight of tetrahydrofuran was added, and the mixture was stirred with a shaker for 2 hours. Then, it separated into a supernatant and a precipitate with a centrifuge, the supernatant was removed, and the precipitate was dried under reduced pressure to obtain titanyl phthalocyanine. The CuKα characteristic X-ray diffraction pattern of this compound showed a maximum diffraction peak at 27.2 degrees as shown in FIG.

【００３９】次に、このチタニルフタロシアニン１重量
部に、実施例１で用いたヒドロキシプロピルメチルセル
ロース１重量部を水４７重量部及びテトラヒドロフラン
５０重量部に溶解させた溶液を添加し、振とう機で２時
間の攪拌を行った後、さらに２時間の超音波分散処理を
行って、電荷発生層用塗液を得た。Next, to 1 part by weight of this titanyl phthalocyanine was added a solution of 1 part by weight of hydroxypropylmethylcellulose used in Example 1 in 47 parts by weight of water and 50 parts by weight of tetrahydrofuran, and the mixture was shaken to obtain 2 parts. After stirring for an hour, ultrasonic dispersion treatment was further performed for 2 hours to obtain a charge generation layer coating liquid.

【００４０】この塗液を用いて、実施例１と同様にして
電荷発生層及び電荷輸送層を作製し、機能分離型の電子
写真用感光体を得た。この感光体の電子写真特性を測定
したところ、帯電電位−１０１０Ｖ，暗減衰８５％，感
度１.２ｌｘ・ｓ と実施例１に比べ、感度が劣ってい
た。Using this coating solution, a charge generation layer and a charge transport layer were prepared in the same manner as in Example 1 to obtain a function-separated type electrophotographic photoreceptor. When the electrophotographic characteristics of this photosensitive member were measured, the charging potential was −1010 V, the dark decay was 85%, and the sensitivity was 1.2 lx · s, which was inferior to Example 1.

【００４１】塗液におけるチタニルフタロシアニンの結
晶状態を調べるため、上記２７.２度に最大の回折ピー
クを示すチタニルフタロシアニン１重量部に、水４７重
量部及びテトラヒドロフラン５０重量部を添加し、上記
塗液作製時と同じ分散処理を行った。その後、溶液を除
去後乾燥して、チタニルフタロシアニン粉末を得た。こ
の化合物のＣｕＫα特性Ｘ線回折図は図２に示すよう
に、明らかに２７.２ 度に最大の回折ピークを示す物と
は異なり、結晶型が変化していることが分かった。In order to examine the crystalline state of titanyl phthalocyanine in the coating liquid, 47 parts by weight of water and 50 parts by weight of tetrahydrofuran were added to 1 part by weight of titanyl phthalocyanine showing the maximum diffraction peak at 27.2 degrees, and the coating liquid was added. The same dispersion treatment as at the time of production was performed. Then, the solution was removed and then dried to obtain a titanyl phthalocyanine powder. As shown in FIG. 2, the CuKα characteristic X-ray diffraction pattern of this compound was found to be different in crystal form from the one clearly showing the maximum diffraction peak at 27.2 degrees.

【００４２】〔実施例２〕合成例で得たチタニルフタロ
シアニン３重量部を遊星ボールミルで２０時間摩砕し
た。このチタニルフタロシアニン３重量部に水７重量部
を添加し、振とう機で２時間の分散処理を行った。さら
に、テトラヒドロフラン１０重量部を添加し、さらに２
時間の分散処理を行った。この時のチタニルフタロシア
ニンのＸ線回折を測定したところ、図１と同様に２７．
２度に最大の回折ピークを有するものであった。この分
散液に、メチルセルロース樹脂（信越化学工業製，メト
ローズＳＭ２５）１重量部を水７９重量部に溶解した溶
液を添加し、振とう機で２時間及び超音波で２時間の分
散処理を行い、電荷発生層用塗液を得た。Example 2 3 parts by weight of titanyl phthalocyanine obtained in the synthesis example was ground for 20 hours in a planetary ball mill. 7 parts by weight of water was added to 3 parts by weight of this titanyl phthalocyanine, and dispersion treatment was carried out for 2 hours on a shaker. Furthermore, 10 parts by weight of tetrahydrofuran is added to further add 2 parts.
The time was dispersed. When X-ray diffraction of titanyl phthalocyanine at this time was measured, it was found to be 27.
It had a maximum diffraction peak at 2 degrees. To this dispersion, a solution prepared by dissolving 1 part by weight of methylcellulose resin (manufactured by Shin-Etsu Chemical Co., Ltd., Metroze SM25) in 79 parts by weight of water was added, and a dispersion treatment was carried out for 2 hours with a shaker and 2 hours with ultrasonic waves. A charge generation layer coating liquid was obtained.

【００４３】この塗液を用いて、実施例１と同様にして
電荷発生層及び電荷輸送層を作製し、機能分離型の電子
写真用感光体を得た。この感光体の電子写真特性を測定
したところ、帯電電位−９８０Ｖ，暗減衰８２％，感度
０.６ｌｘ・ｓ と高感度が得られた。Using this coating solution, a charge generation layer and a charge transport layer were prepared in the same manner as in Example 1 to obtain a function-separated type electrophotographic photoreceptor. When the electrophotographic characteristics of this photosensitive member were measured, a high charging sensitivity of −980 V, dark decay of 82%, and sensitivity of 0.6 lx · s were obtained.

【００４４】[0044]

【発明の効果】従来の技術では、分散媒に有機溶剤を使
用することによって、電子写真用感光体の電荷発生物質
として高感度である結晶型のフタロシアニン化合物は結
晶転移を生じ、高感度が得られなくなるという欠点があ
った。According to the prior art, by using an organic solvent as a dispersion medium, a crystalline phthalocyanine compound, which is highly sensitive as a charge generating substance of an electrophotographic photoreceptor, undergoes a crystal transition to obtain high sensitivity. There was a drawback that you couldn't.

【００４５】本発明によれば、高感度を有する結晶型を
転移させずに電荷発生層用塗液が作製できるために、高
感度を有する機能分離型の電子写真用感光体を得ること
ができる。According to the present invention, the charge generation layer coating liquid can be prepared without transferring the crystal form having high sensitivity, so that the function-separated electrophotographic photoreceptor having high sensitivity can be obtained. .

【図面の簡単な説明】[Brief description of drawings]

【図１】実施例１におけるブラッグ角２７.２ 度に最大
ピークを有するチタニルフタロシアニン化合物のＣｕＫ
α特性Ｘ線回折図。FIG. 1 is CuK of a titanyl phthalocyanine compound having a maximum peak at a Bragg angle of 27.2 degrees in Example 1.
α characteristic X-ray diffraction diagram.

【図２】比較例におけるブラッグ角２７.２ 度に最大ピ
ークを有しないチタニルフタロシアニン化合物のＣｕＫ
α特性Ｘ線回折図。FIG. 2 is a CuK of a titanyl phthalocyanine compound having no maximum peak at a Bragg angle of 27.2 degrees in a comparative example.
α characteristic X-ray diffraction diagram.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 稔幸 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 岩柳 隆夫 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 勝谷 康夫 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社山崎工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Kobayashi 7-1-1 Omika-cho, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Takao Iwayanagi 7-chome, Omika-cho, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Yasuo Katsuya 4-13-1, Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (11)

【特許請求の範囲】[Claims] 【請求項１】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体の電荷発
生層用塗液において、該塗液がフタロシアニン化合物の
水ペーストに有機溶剤及び水溶性樹脂溶液を配合してな
ることを特徴とする機能分離型電子写真用感光体の電荷
発生層用塗液。1. A coating liquid for a charge generation layer of a function-separated electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, wherein the coating liquid is a water paste of a phthalocyanine compound. A coating liquid for a charge generation layer of a function-separated type electrophotographic photoreceptor, which is obtained by mixing an organic solvent and a water-soluble resin solution. 【請求項２】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体の電荷発
生層用塗液において、該塗液がチタニルフタロシアニン
の水ペーストに有機溶剤及び水溶性樹脂溶液を配合して
なり、該チタニルフタロシアニンがＣｕＫα特性Ｘ線回
折においてブラッグ角（２θ±０.２度）２７.２度に最
大の回折ピークを有することを特徴とする機能分離型電
子写真用感光体の電荷発生層用塗液。2. A coating liquid for a charge generation layer of a function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, wherein the coating liquid is a water paste of titanyl phthalocyanine. And an organic solvent and a water-soluble resin solution are blended, and the titanyl phthalocyanine has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees in CuKα characteristic X-ray diffraction. A coating liquid for the charge generation layer of a function-separated electrophotographic photoreceptor. 【請求項３】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体の電荷発
生層用塗液において、該塗液がバナジルフタロシアニン
の水ペーストに有機溶剤及び水溶性樹脂溶液を配合して
なり、該バナジルフタロシアニンがＣｕＫα特性Ｘ線回
折においてブラッグ角（２θ±０.２度）２７.２度に最
大の回折ピークを有することを特徴とする機能分離型電
子写真用感光体の電荷発生層用塗液。3. A coating liquid for a charge generation layer of a function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, wherein the coating liquid is a water paste of vanadyl phthalocyanine. Which is blended with an organic solvent and a water-soluble resin solution, wherein the vanadyl phthalocyanine has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees in CuKα characteristic X-ray diffraction. A coating liquid for the charge generation layer of a function-separated electrophotographic photoreceptor. 【請求項４】前記有機溶剤がメチルエチルケトンあるい
はテトラヒドロフランであることを特徴とする請求項２
及び請求項３記載の機能分離型電子写真用感光体の電荷
発生層用塗液。4. The organic solvent is methyl ethyl ketone or tetrahydrofuran.
And a coating liquid for the charge generation layer of the electrophotographic photoreceptor for functional separation according to claim 3. 【請求項５】前記水溶性樹脂が、セルロース樹脂である
ことを特徴とする請求項２及び請求項３記載の機能分離
型電子写真用感光体の電荷発生層用塗液。5. The coating liquid for a charge generating layer of a function-separated type electrophotographic photoreceptor according to claim 2, wherein the water-soluble resin is a cellulose resin. 【請求項６】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体の電荷発
生層用塗液の製法において、該塗液がフタロシアニン化
合物の水ペーストに有機溶剤及び水溶性樹脂溶液を配合
することを特徴とする機能分離型電子写真用感光体の電
荷発生層用塗液の製法。6. A method for producing a coating liquid for a charge generation layer of a function-separated electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, wherein the coating liquid is a phthalocyanine compound. A method for producing a coating liquid for a charge generation layer of a function-separated electrophotographic photoreceptor, which comprises mixing an organic solvent and a water-soluble resin solution in a water paste. 【請求項７】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体におい
て、該電荷発生層の塗液がフタロシアニン化合物の水ペ
ーストに有機溶剤及び水溶性樹脂溶液を配合してなるこ
とを特徴とする機能分離型電子写真用感光体。7. A function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, wherein the coating solution for the charge generation layer is a water paste of a phthalocyanine compound and an organic solvent. And a function-separated type electrophotographic photoreceptor, which comprises a water-soluble resin solution. 【請求項８】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体におい
て、該電荷発生層の塗液がチタニルフタロシアニンの水
ペーストに有機溶剤及び水溶性樹脂溶液を配合してな
り、該チタニルフタロシアニンがＣｕＫα特性Ｘ線回折
においてブラッグ角（２θ±０.２度）２７.２度に最大
の回折ピークを有することを特徴とする機能分離型電子
写真用感光体。8. A function-separated type electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, wherein the coating solution for the charge generation layer is a water paste of titanyl phthalocyanine and an organic solvent. And a water-soluble resin solution, wherein the titanyl phthalocyanine has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees in CuKα characteristic X-ray diffraction. Electrophotographic photoreceptor. 【請求項９】導電性支持体上に電荷発生層、該層上に電
荷輸送層を有する機能分離型電子写真用感光体におい
て、該電荷発生層の塗液がバナジルフタロシアニンの水
ペーストに有機溶剤及び水溶性樹脂溶液を配合してな
り、該バナジルフタロシアニンがＣｕＫα特性Ｘ線回折
においてブラッグ角（２θ±０.２度）２７.２度に最大
の回折ピークを有することを特徴とする機能分離型電子
写真用感光体。9. In a function-separated electrophotographic photoreceptor having a charge generation layer on a conductive support and a charge transport layer on the layer, the coating solution for the charge generation layer is a water paste of vanadyl phthalocyanine and an organic solvent. And a water-soluble resin solution, wherein the vanadyl phthalocyanine has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees in CuKα characteristic X-ray diffraction. Electrophotographic photoreceptor. 【請求項１０】前記有機溶剤がメチルエチルケトンある
いはテトラヒドロフランであることを特徴とする請求項
８及び請求項９記載の機能分離型電子写真用感光体。10. The function-separated type electrophotographic photoreceptor according to claim 8, wherein the organic solvent is methyl ethyl ketone or tetrahydrofuran. 【請求項１１】前記水溶性樹脂が、セルロース樹脂であ
ることを特徴とする請求項８及び請求項９記載の機能分
離型電子写真用感光体。11. The function-separated type electrophotographic photoconductor according to claim 8, wherein the water-soluble resin is a cellulose resin.