JP3953072B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus Download PDF

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JP3953072B2
JP3953072B2 JP2005110940A JP2005110940A JP3953072B2 JP 3953072 B2 JP3953072 B2 JP 3953072B2 JP 2005110940 A JP2005110940 A JP 2005110940A JP 2005110940 A JP2005110940 A JP 2005110940A JP 3953072 B2 JP3953072 B2 JP 3953072B2
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electrophotographic
photosensitive member
electrophotographic photosensitive
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孝和 田中
浩敏 上杉
由香 石塚
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Description

本発明は電子写真感光体、及び該電子写真感光体を有するプロセスカートリッジ及び電子写真装置に関し、詳しくは特定の樹脂を含有する表面層を有する電子写真感光体、及び該電子写真感光体を有するプロセスカートリッジ及び電子写真装置に関する。   The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus, and more specifically, an electrophotographic photosensitive member having a surface layer containing a specific resin, and a process having the electrophotographic photosensitive member. The present invention relates to a cartridge and an electrophotographic apparatus.

電子写真方法は、画像露光の間に受けた照射量に応じて電気抵抗が変化しかつ暗所では絶縁性の物質をコーティングした支持体よりなる光導電性材料を用いる(特許文献1参照)。この光導電性材料を用いた電子写真感光体に要求される基本的な特性としては(1)暗所で適当な電位に帯電できること、(2)暗所において電位の逸散が少ないこと及び(3)光照射によって速やかに電荷を逸散せしめることなどが挙げられる。   The electrophotographic method uses a photoconductive material comprising a support that is coated with an insulating substance in a dark place and whose electric resistance changes according to the dose received during image exposure (see Patent Document 1). Basic characteristics required for an electrophotographic photosensitive member using this photoconductive material are (1) that it can be charged to an appropriate potential in a dark place, (2) that there is little potential dissipation in the dark place, and ( 3) The charge can be quickly dissipated by light irradiation.

従来より電子写真感光体としてはセレン、酸化亜鉛及び硫化カドミウムなどの無機光導電性化合物を主成分とする感光層を有する無機感光体が広く使用されてきた。しかし、これらは前記(1)〜(3)の条件は満足するが、熱安定性、耐湿性、耐久性や生産性において必ずしも満足できるものではなかった。   Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide and cadmium sulfide has been widely used. However, these satisfy the conditions (1) to (3), but are not always satisfactory in terms of thermal stability, moisture resistance, durability and productivity.

無機感光体の欠点を克服する目的で様々な有機光導電性化合物を主成分とする電子写真感光体の開発が近年盛んに行われている。   In order to overcome the disadvantages of inorganic photoreceptors, electrophotographic photoreceptors based on various organic photoconductive compounds as main components have been actively developed in recent years.

更に、有機光導電性化合物はその化合物によって電子写真感光体の感光波長域を自由に選択することが可能であり、例えばアゾ顔料では可視領域で高感度を示す物質が開示されており(特許文献2、3参照)、また赤外領域まで感度を有する化合物が示されている(特許文献4、5参照)。   Furthermore, the organic photoconductive compound can freely select the photosensitive wavelength region of the electrophotographic photosensitive member depending on the compound. For example, an azo pigment has been disclosed as a substance exhibiting high sensitivity in the visible region (Patent Literature). 2 and 3), and compounds having sensitivity to the infrared region are shown (see Patent Documents 4 and 5).

これらの材料のうち赤外領域に感度を示すものは近年進歩の著しいレーザービームプリンター(以下LBPと略す)やLEDプリンターに使用されその需要頻度は高くなってきている。   Among these materials, those showing sensitivity in the infrared region are used in laser beam printers (hereinafter abbreviated as LBP) and LED printers that have made remarkable progress in recent years, and the frequency of demand thereof has increased.

これら有機光導電性化合物を用いた電子写真感光体は電気的及び機械的双方の特性を満足させるために、電荷輸送層と電荷発生層を積層させた機能分離型の感光体として利用される場合が多い。一方、当然のことながら、電子写真感光体には適用される電子写真プロセスに応じた感度や電気的特性、更には光学的特性を備えていることが要求される。   When an electrophotographic photoreceptor using these organic photoconductive compounds is used as a function-separated photoreceptor in which a charge transport layer and a charge generation layer are laminated in order to satisfy both electrical and mechanical properties. There are many. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process.

特に、繰り返し使用される電子写真感光体においては、その電子写真感光体表面にはコロナまたは直接帯電、画像露光、トナー現像、転写工程及び表面クリーニングなどの電気的及び機械的外力が直接加えられるため、それらに対する耐久性も要求される。   In particular, in electrophotographic photoreceptors that are used repeatedly, electrical and mechanical external forces such as corona or direct charging, image exposure, toner development, transfer process and surface cleaning are directly applied to the surface of the electrophotographic photoreceptor. , Durability against them is also required.

具体的には、帯電時のオゾンや窒素酸化物による電気的劣化や、帯電時の放電やクリーニング部材の摺擦によって表面が摩耗したり傷が発生したりする機械的劣化、また電気的劣化に対する耐久性が求められている。   Specifically, it is suitable for electrical deterioration due to ozone and nitrogen oxides during charging, mechanical deterioration in which the surface is worn or scratched due to discharge during charging and rubbing of the cleaning member, and electrical deterioration. Durability is required.

電気的劣化は光が照射した部分にキャリアーが滞留し光が照射していない部分と電位差が生じる現象が特に問題であり、これはフォトメモリーとして生じる。   The electrical deterioration is particularly a phenomenon in which a carrier is accumulated in a portion irradiated with light and a potential difference is generated from a portion not irradiated with light, which occurs as a photo memory.

無機感光体と異なり物質的に柔らかいものが多い有機感光体は、機械的劣化に対する耐久性が劣り、耐久性向上は特に切望されているものである。   Unlike inorganic photoreceptors, organic photoreceptors that are often soft in material are poor in durability against mechanical deterioration, and improvement in durability is particularly desired.

上記のような感光体に要求される耐久特性を満足させるためにいろいろ試みがなされてきた。   Various attempts have been made to satisfy the durability characteristics required for the photoreceptor as described above.

表面層によく使用され摩耗性及び電気特性に良好な樹脂としてはビスフェノールAを骨格とするポリカーボネート樹脂が注目されているが、前述したような問題点すべてを解決できるわけでもなく、次のような問題点を有している。   A polycarbonate resin having a bisphenol A skeleton as a resin that is often used for the surface layer and has good wear characteristics and electrical properties has attracted attention. Has a problem.

(1)溶解性に乏しくジクロロメタンや1,2−ジクロロエタンなどのハロゲン化脂肪族炭化水素類の一部にしか良好な溶解性を示さない上、これらの溶剤は低沸点のため、これらの溶剤で調製した塗工液を用いて感光体を製造すると塗工面が白化し易い。塗工液の固形分管理などにも手間がかかる。   (1) It has poor solubility and exhibits good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane, and these solvents have low boiling points. When a photoreceptor is manufactured using the prepared coating solution, the coated surface is likely to be whitened. It also takes time to manage the solid content of the coating liquid.

(2)ハロゲン化脂肪族炭化水素類以外の溶剤に対してはテトラヒドラフラン、ジオキサン、シクロヘキサンノンあるいはそれらの混合溶剤に一部可溶であるが、その溶液は数日でゲル化するなど経時性が悪く感光体製造には不向きである。   (2) Solvents other than halogenated aliphatic hydrocarbons are partially soluble in tetrahydrafuran, dioxane, cyclohexane, or mixed solvents thereof, but the solution gels in several days. It is not suitable for photoconductor production due to poor properties.

(3)更に上記(1)及び(2)が改善されたとしても、ビスフェノールAを骨格とするポリカーボネート樹脂にはソルベントクラックが発生し易い。   (3) Even if the above (1) and (2) are further improved, a solvent crack is likely to occur in the polycarbonate resin having bisphenol A as a skeleton.

(4)加えて、従来のポリカーボネート樹脂では該樹脂で形成された被膜に潤滑性がないため感光体に傷が付き易く、電子写真感光体の摩耗量を低くするようなクリーニング設定では画像欠陥になったり、クリーニングブレードの早期の劣化によるクリーニング不良やトナー融着などが生じてしまうことがあった。   (4) In addition, with the conventional polycarbonate resin, the coating formed with the resin is not lubricious, so the photoconductor is easily scratched, and the cleaning setting that reduces the wear amount of the electrophotographic photoconductor causes image defects. Or cleaning failure due to early deterioration of the cleaning blade or toner fusion may occur.

前記(1)及び(2)に挙げた溶液安定性についてはポリマーの構造単位として嵩高いシクロヘキシレン基を有するポリカーボネートZ樹脂を使用するか、ビスフェノールZやビスフェノールCなどと共重合させることによって解決されてきた。   The solution stability mentioned in the above (1) and (2) can be solved by using a polycarbonate Z resin having a bulky cyclohexylene group as a polymer structural unit or by copolymerizing with bisphenol Z or bisphenol C. I came.

また、ソルベントクラックについてもシリコン変成ポリカーボネート、エーテル変成ポリカーボネートを用いることにより解決することが可能である(特許文献6、7参照)。ところが、これら変成ポリカーボネートは従来のポリカーボネート樹脂に比べソルベントクラックを対策するためにポリマー内の内部応力に対して柔軟性を持たしている構造をとっている結果、重合体本体の機械的強度が低下するという欠点があった。   Solvent cracks can also be solved by using silicon-modified polycarbonate or ether-modified polycarbonate (see Patent Documents 6 and 7). However, these modified polycarbonates have a structure that has flexibility against internal stress in the polymer to prevent solvent cracks compared to conventional polycarbonate resins, resulting in a decrease in the mechanical strength of the polymer body. There was a drawback of doing.

更に近年、帯電部材に直接電圧をかけ電子写真感光体に電荷を印加する直接帯電方式が主流となりつつある(特許文献8、9参照)。   Furthermore, in recent years, a direct charging method in which a voltage is directly applied to a charging member and a charge is applied to an electrophotographic photosensitive member is becoming mainstream (see Patent Documents 8 and 9).

これは、導電ゴムなどで構成されたローラー状の帯電部材を直接電子写真感光体に当接させ電荷を印加する方法であり、スコロトロンなどに比べオゾン発生量が格段に少ない、スコロトロンは帯電器に流す電流の80%前後はシールドに流れるため浪費されるのに対して、直接帯電はこの浪費分がなく非常に経済的である、などのメリットを持つ。   This is a method in which a roller-shaped charging member made of conductive rubber or the like is directly brought into contact with the electrophotographic photosensitive member to apply a charge. Ozone generation is significantly less than that of scorotron, etc. Around 80% of the current that flows is wasted because it flows to the shield, whereas direct charging has the merit of being very economical because there is no wasted amount.

しかし、直接帯電はパッシェン則に従う放電による帯電のため帯電安定性が非常に悪いという欠点を持つ。この対策として直流電圧に交流電圧を重畳させた、いわゆるAC/DC帯電方式が考案されている(特許文献10参照)。   However, direct charging has the disadvantage that the charging stability is very poor due to charging by discharge according to Paschen's law. As a countermeasure, a so-called AC / DC charging method in which an AC voltage is superimposed on a DC voltage has been devised (see Patent Document 10).

この帯電方式により帯電時の安定性は良化したがACを重畳するために電子写真感光体表面の放電量は大幅に増大するため、電子写真感光体の削れ量が増加してしまうという欠点を新たに生じてしまい、機械的強度のみならず電気的強度も要求されるようになってきた。
米国特許第2297691号公報 特開昭61−272754号公報 特開昭56−167759号公報 特開昭57−19576号公報 特開昭61−228453号公報 特開平6−51544号公報 特開平6−75415号公報 特開昭57−17826号公報 特開昭58−40566号公報 特開昭63−149668号公報
Although this charging system improves the stability during charging, the amount of discharge on the surface of the electrophotographic photosensitive member is greatly increased due to the superposition of AC, so that the amount of abrasion of the electrophotographic photosensitive member increases. It has arisen newly, and not only mechanical strength but also electrical strength has been demanded.
US Patent No. 2,297,691 JP-A-61-272754 JP 56-167759 A JP 57-19576 A Japanese Patent Laid-Open No. 61-228453 JP-A-6-51544 JP-A-6-75415 JP 57-17826 A JP 58-40566 A JP-A 63-149668

本発明の目的は、耐ソルベントクラック性及び機械的強度に優れると共に、耐電気特性が良好であり、高感度かつフォトメモリーの少ない電子写真感光体、及び該電子写真感光体を有するプロセスカートリッジ及び電子写真装置を提供することにある。   An object of the present invention is to provide an electrophotographic photoreceptor excellent in solvent crack resistance and mechanical strength, having good electrical resistance, high sensitivity and low photomemory, and a process cartridge and an electronic device having the electrophotographic photoreceptor It is to provide a photographic apparatus.

本発明は、支持体及び感光層を有する電子写真感光体において、該電子写真感光体の表面層が、下記式(3)で示される繰り返し単位を有するポリエステル樹脂を含有することを特徴とする電子写真感光体である。   The present invention provides an electrophotographic photosensitive member having a support and a photosensitive layer, wherein the surface layer of the electrophotographic photosensitive member contains a polyester resin having a repeating unit represented by the following formula (3). It is a photographic photoreceptor.

Figure 0003953072
(式(3)中、Arは置換基を有しても良いアルキレン基を示し、RからR12は水素原子、ハロゲン原子または置換基を有しても良いアルキル基を示す。)
Figure 0003953072
(In formula (3), Ar 2 represents an alkylene group which may have a substituent, and R 9 to R 12 represent a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.)

また、本発明は、前記ポリエステル樹脂が、前記式(3)で示される繰り返し単位と下記式(4)で示される繰り返し単位とを有する共重合体である請求項1に記載の電子写真感光体である。式(3)で示される繰り返し単位の重合体、または式(3)と式(4)で示される繰り返し単位の共重合体を、以下本発明の重合体という。   The electrophotographic photoreceptor according to claim 1, wherein the polyester resin is a copolymer having a repeating unit represented by the formula (3) and a repeating unit represented by the following formula (4). It is. The polymer of the repeating unit represented by the formula (3) or the copolymer of the repeating unit represented by the formulas (3) and (4) is hereinafter referred to as a polymer of the present invention.

Figure 0003953072
(式(4)中、Arは置換されても良いアルキレン基を示す。)
Figure 0003953072
(In formula (4), Ar 3 represents an optionally substituted alkylene group.)

また、本発明は、上記電子写真感光体を有するプロセスカートリッジ及び電子写真装置である。   The present invention also provides a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

本発明によれば、機械的強度を損なうことなく優れた耐ソルベントクラック性を有し、更に機械的強度が強く、かつ直接帯電による放電に対する帯電気特性が良好であり、フォトメモリーの低減した電子写真感光体、及び該電子写真感光体を有するプロセスカートリッジ及び電子写真装置を提供することが可能となった。   According to the present invention, it has excellent solvent crack resistance without impairing mechanical strength, and further has high mechanical strength, good electrical characteristics against discharge due to direct charging, and reduced electron memory. It has become possible to provide a photographic photoreceptor, and a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor.

上記式(3)及び(4)におけるアルキル基としては、メチル、エチル、プロピル及びブチルなどの基が挙げられ、アルキレン基としては、メチレン、エチレン、プロピレン及びブチレンなどの基が挙げられ、ハロゲン原子としては、フッ素及び塩素などの原子が挙げられる。   Examples of the alkyl group in the above formulas (3) and (4) include groups such as methyl, ethyl, propyl, and butyl. Examples of the alkylene group include groups such as methylene, ethylene, propylene, and butylene. Include atoms such as fluorine and chlorine.

また、上記アルキレン基及びアルキル基が有していてもよい置換基としては、メチル、エチル、プロピルなどのアルキル基及びフッ素及び塩素などのハロゲン原子などが挙げられる。   In addition, examples of the substituent that the alkylene group and the alkyl group may have include an alkyl group such as methyl, ethyl, and propyl, and a halogen atom such as fluorine and chlorine.

以下に、上記式(3)及び(4)で示される繰り返し単位の具体例を示すが、これらに限られるものではない。   Specific examples of the repeating unit represented by the above formulas (3) and (4) are shown below, but are not limited thereto.

Figure 0003953072
Figure 0003953072

Figure 0003953072
Figure 0003953072

Figure 0003953072
Figure 0003953072

本発明の電子写真感光体は、特に優れた機械的強度と耐ソルベントクラック性を有し、かつ耐電気特性にも優れた良好な電子写真特性を持つものである。   The electrophotographic photosensitive member of the present invention has excellent electrophotographic characteristics, particularly excellent mechanical strength and solvent crack resistance, and also excellent electrical resistance characteristics.

本発明の重合体は、剛直な性質を有するテレフタル酸構造と柔軟な性質(いわゆる靱性)を有する脂肪族炭化水素構造を同時に有するため、硬いが脆い剛直ユニットの性質にしなやかさ(いわゆる靭性)が加わることで優れた機械的強度を有するとともに耐ソルベントクラック性が良化するに至ったものと考えられる。   Since the polymer of the present invention has a rigid terephthalic acid structure having a rigid property and an aliphatic hydrocarbon structure having a flexible property (so-called toughness) at the same time, it has flexibility (so-called toughness) in the properties of a hard but brittle rigid unit. It is considered that the addition has excellent mechanical strength and improved solvent crack resistance.

本発明の重合体は、主鎖の繰り返し単位が単一のもので構成される重合体でも、2種類以上の別種の繰り返し単位からなる共重合体でも良い。   The polymer of the present invention may be a polymer composed of a single main chain repeating unit or a copolymer composed of two or more different types of repeating units.

また、ポリカーボネートやポリアリレートなどの既存の樹脂との共重合体またはアロイ(ブレンドも含む)として使用しても良い。   Further, it may be used as a copolymer or alloy (including a blend) with an existing resin such as polycarbonate or polyarylate.

ただし、その場合、本発明の重合体の割合が10mol%以上であることが望ましい。   However, in that case, it is desirable that the ratio of the polymer of the present invention is 10 mol% or more.

本発明の重合体は、テレフタル酸またはイソフタル酸のカルボン酸成分と任意の脂肪族ジオールとを重合させることにより得られる。このときカルボン酸成分は、酸クロライドとして使用するのが好ましい。   The polymer of the present invention can be obtained by polymerizing a carboxylic acid component of terephthalic acid or isophthalic acid and an arbitrary aliphatic diol. At this time, the carboxylic acid component is preferably used as an acid chloride.

以下、本発明の電子写真感光体の構成について説明する。   Hereinafter, the configuration of the electrophotographic photoreceptor of the present invention will be described.

本発明の電子写真感光体は、感光層が電荷輸送材料と電荷発生材料を同一の層に含有する単層型であっても、電荷輸送層と電荷発生層に分離した積層型でも良いが、電子写真特性上は積層型が好ましい。   In the electrophotographic photoreceptor of the present invention, the photosensitive layer may be a single layer type in which the charge transport material and the charge generation material are contained in the same layer, or may be a stacked type in which the charge transport layer and the charge generation layer are separated, From the viewpoint of electrophotographic characteristics, a laminated type is preferable.

使用する支持体は導電性を有するものであればよく、アルミニウム及びステンレスなどの金属、あるいは導電層を設けた金属、紙及びプラスチックなどが挙げられ、形状はシート状及び円筒状などが挙げられる。   The support to be used is not particularly limited as long as it has conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, paper, and plastics, and examples of the shape include a sheet shape and a cylindrical shape.

LBPなど画像入力がレーザー光の場合は散乱による干渉縞防止、また支持体の傷を被覆することを目的とした導電層を設けても良い。これは、カーボンブラック及び金属粒子などの導電性粉体をバインダー樹脂に分散させて形成することができる。導電層の膜厚は5〜40μmであることが好ましく、10〜30μmであることがより好ましい。   When the image input is laser light such as LBP, a conductive layer may be provided for the purpose of preventing interference fringes due to scattering and covering scratches on the support. This can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, and more preferably 10 to 30 μm.

その上に接着機能を有する中間層を設ける。中間層の材料としてはポリアミド、ポリビニルアルコール、ポリエチレンオキシド、エチルセルロース、カゼイン、ポリウレタン及びポリエーテルウレタンなどが挙げられる。これらは適当な溶剤に溶解して塗布される。中間層の膜厚は0.05〜5μmであることが好ましく、0.3〜1μmであることがより好ましい。   An intermediate layer having an adhesive function is provided thereon. Examples of the material for the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These are dissolved in an appropriate solvent and applied. The thickness of the intermediate layer is preferably 0.05 to 5 μm, and more preferably 0.3 to 1 μm.

中間層の上には電荷発生層が形成される。本発明に用いられる電荷発生材料としてはセレンーテルル、ピリリウム、チアピリリウム系染料、フタロシアニン、アントアントロン、ジベンズピレンキノン、トリスアゾ、シアニン、ジスアゾ、モノアゾ、インジゴ、キナクリドン及び非対称キノシアニン系などの顔料が挙げられる。機能分離型の場合、電荷発生層は前記電荷発生材料を0.3〜4倍量のバインダー樹脂及び溶剤と共にホモジナイザー、超音波分散、ボールミル、振動ボールミル、サンドミル、アトライター、ロールミル及び液衝突型高速分散機などの方法でよく分散し、分散液を塗布し、乾燥させて形成される。電荷発生層の膜厚は5μm以下であることが好ましく、0.1〜2μmであることがより好ましい。   A charge generation layer is formed on the intermediate layer. Examples of the charge generating material used in the present invention include selenium tellurium, pyrylium, thiapyrylium dyes, phthalocyanine, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments. In the case of the function separation type, the charge generation layer is composed of the above charge generation material with a binder resin and a solvent in an amount of 0.3 to 4 times, a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, and a liquid collision type high speed. It is formed by dispersing well by a method such as a disperser, applying a dispersion, and drying. The film thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.1 to 2 μm.

電荷輸送層は、主として電荷輸送材料とバインダー樹脂としての本発明の重合体とを溶剤中に溶解させた塗料を塗工乾燥して形成する。用いられる電荷輸送材料としてはトリアリールアミン系化合物、ヒドラゾン化合物、スチルベン化合物、ピラゾリン系化合物、オキサゾール系化合物、トリアリルメタン系化合物及びチアゾール系化合物などが挙げられる。   The charge transport layer is formed by applying and drying a paint in which a charge transport material and the polymer of the present invention as a binder resin are dissolved in a solvent. Examples of the charge transport material used include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds, and thiazole compounds.

これらは0.5〜2倍量のバインダー樹脂と組み合わされ塗工し、乾燥させて電荷輸送層を形成する。電荷輸送層の膜厚は5〜40μmであることが好ましく、15〜30μmであることがより好ましい。   These are combined with 0.5 to 2 times the amount of binder resin, applied, and dried to form a charge transport layer. The film thickness of the charge transport layer is preferably 5 to 40 μm, and more preferably 15 to 30 μm.

図1に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を示す。   FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

図において、1はドラム状の本発明の電子写真感光体であり、軸2を中心に矢印方向に所定の周速度で回転駆動される。感光体1は、回転過程において、一次帯電手段3によりその周面に正または負の所定電位の均一帯電を受け、次いで、スリット露光やレーザービーム走査露光などの露光手段(不図示)からの露光光4を受ける。こうして感光体1の周面に静電潜像が順次形成されていく。   In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotation process, the photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 3, and then exposed from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Receive light 4. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1.

形成された静電潜像は、次いで現像手段5によりトナー現像され、現像されたトナー現像像は、不図示の給紙部から感光体1と転写手段6との間に感光体1の回転と同期取り出されて給紙された転写材7に、転写手段6により順次転写されていく。   The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner developed image is rotated between the photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The image is sequentially transferred by the transfer means 6 to the transfer material 7 that is synchronously taken out and fed.

像転写を受けた転写材7は、感光体面から分離されて像定着手段8へ導入されて像定着を受けることにより複写物(コピー)として装置外へプリントアウトされる。   The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, thereby being printed out as a copy (copy).

像転写後の感光体1の表面は、クリーニング手段9によって転写残りトナーの除去を受けて清浄面化され、更に前露光手段(不図示)からの前露光光10により除電処理された後、繰り返し画像形成に使用される。なお、一次帯電手段3が帯電ローラーなどを用いた接触帯電手段である場合は、前露光は必ずしも必要ではない。   After the image transfer, the surface of the photoreceptor 1 is cleaned by removing the transfer residual toner by the cleaning unit 9 and further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown), and then repeatedly. Used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.

本発明においては、上述の電子写真感光体1、一次帯電手段3、現像手段5及びクリーニング手段9などの構成要素のうち、複数のものをプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンターなどの電子写真装置本体に対して着脱自在に構成しても良い。例えば、一次帯電手段3、現像手段5及びクリーニング手段9の少なくとも1つを感光体1と共に一体に支持してカートリッジ化して、装置本体のレール12などの案内手段を用いて装置本体に着脱自在なプロセスカートリッジ11とすることができる。   In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging unit 3, developing unit 5, and cleaning unit 9 are integrally coupled as a process cartridge. May be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photosensitive member 1 to form a cartridge, and is detachable from the apparatus main body using guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be obtained.

また、露光光4は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読取り、信号化し、この信号に従って行われるレーザービームの走査、LEDアレイの駆動及び液晶シャッターアレイの駆動などにより照射される光である。   Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. The light is emitted by driving the LED array and the liquid crystal shutter array.

本発明の電子写真感光体は電子写真複写機に利用するのみならず、レーザービームプリンター、CRTプリンター、LEDプリンター、液晶プリンター及びレーザー製版など電子写真応用分野にも広く用いることができる。   The electrophotographic photosensitive member of the present invention can be used not only in electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.

(合成例1)
ベンゼンジメタノール(1.0mol)、エチレングリコール(1.0mol)、テレフタル酸(1.0mol)及びイソフタル酸(1.0mol)をSUS製容器に入れ、250℃で加熱攪拌した。1時間後、反応温度を280℃まで上昇させ、更に2時間加熱攪拌した。
(Synthesis Example 1)
Benzene dimethanol (1.0 mol), ethylene glycol (1.0 mol), terephthalic acid (1.0 mol), and isophthalic acid (1.0 mol) were placed in a SUS container and heated and stirred at 250 ° C. After 1 hour, the reaction temperature was raised to 280 ° C., and the mixture was further heated and stirred for 2 hours.

放冷後、ジクロロメタン1.5リットルに溶解し、メタノールから再沈殿させた。沈殿物を濾取し、乾燥させて、無色のポリマーを得た(下記繰り返し単位1−1を有する樹脂)。   After cooling, it was dissolved in 1.5 liters of dichloromethane and reprecipitated from methanol. The precipitate was collected by filtration and dried to obtain a colorless polymer (resin having the following repeating unit 1-1).

Figure 0003953072
Figure 0003953072

最終収率は80%であった。   The final yield was 80%.

以下実施例に従って説明する。実施例中「部」は重量部を示す。また、実施例中の樹脂No.1〜3は前記合成例と同様の方法で重合し、例示化合物に対応した構造を有する樹脂を合成した。   A description will be given below in accordance with examples. In the examples, “parts” represents parts by weight. Moreover, resin No. in an Example. 1 to 3 were polymerized in the same manner as in the above synthesis examples to synthesize resins having structures corresponding to the exemplified compounds.

(実施例1)
φ30mm、長さ254mmのアルミニウムシリンダーを支持体とし、以下の材料より構成される塗料を支持体上に浸漬コーティング法で塗布し、140℃で30分熱硬化して、膜厚17μmの導電層を形成した。
Example 1
Using a 30 mm diameter, 254 mm long aluminum cylinder as a support, a coating composed of the following materials is applied onto the support by a dip coating method and thermally cured at 140 ° C. for 30 minutes to form a 17 μm thick conductive layer. Formed.

導電性顔料:SnOコート処理硫酸バリウム 10部
抵抗調節用顔料:酸化チタン 2部
バインダー樹脂:フェノール樹脂 6部
レベリング材:シリコーンオイル 0.001部
溶剤:メタノール、メトキシプロパノール0.2/0.8 20部
Conductive pigment: SnO 2 coated treated 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 20 copies

次に、この上にNメトキシメチル化ナイロン3部及び共重合ナイロン3部をメタノール70部及びn−ブタノール30部の混合溶媒に溶解した溶液を浸漬コーティング法で塗布し、乾燥させて、膜厚0.7μmの中間層を形成した。   Next, a solution obtained by dissolving 3 parts of N methoxymethylated nylon and 3 parts of copolymer nylon in a mixed solvent of 70 parts of methanol and 30 parts of n-butanol is applied by dip coating method and dried. A 0.7 μm intermediate layer was formed.

次に、CuKα特性X線回折のブラッグ角の2θ±0.2°の9.0°、14.2°、23.9°及び27.1°に強いピークを有するオキシチタニウムフタロシアニン(TiOPc)4部、ポリビニルブチラール樹脂(商品名:エスレックBM2、積水化学製)2部及びシクロヘキサノン60部をφ1mmガラスビーズを用いたサンドミル装置で4時間分散した後、エチルアセテート100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、乾燥させて、膜厚0.3μmの電荷発生層を形成した。   Next, oxytitanium phthalocyanine (TiOPc) 4 having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the Bragg angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction. Parts, polyvinyl butyral resin (trade name: ESREC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 60 parts of cyclohexanone were dispersed for 4 hours in a sand mill using φ1 mm glass beads, and then 100 parts of ethyl acetate was added to disperse the charge generation layer. A liquid was prepared. This was applied by a dip coating method and dried to form a charge generation layer having a thickness of 0.3 μm.

次に、前記合成例と同様の方法で合成した表1の樹脂No.1記載の重合体10部及び下記の化合物8部(CT−1/CT−2=9/1)をモノクロロベンゼン50部及びジクロロメタン50部の混合溶媒に溶解した。   Next, the resin No. of Table 1 synthesized by the same method as in the above synthesis example. 10 parts of the polymer described in 1 and 8 parts of the following compound (CT-1 / CT-2 = 9/1) were dissolved in a mixed solvent of 50 parts of monochlorobenzene and 50 parts of dichloromethane.

Figure 0003953072
Figure 0003953072

この塗料を浸漬コーティング法で塗布し、120℃で1時間乾燥させて、膜厚24μmの電荷輸送層を形成した。   This paint was applied by a dip coating method and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 24 μm.

次に、評価について説明する。   Next, evaluation will be described.

作成した感光体をヒューレットパッカード製LBP「レーザージェット4plus」(プロセススピード71mm/sec)を改造したものに装着した。改造は、帯電時のピーク間電圧が30%増加するように設定を変更した。   The created photoreceptor was mounted on a modified Hewlett-Packard LBP “Laser Jet 4 plus” (process speed 71 mm / sec). In the modification, the setting was changed so that the peak-to-peak voltage during charging increased by 30%.

作成した電子写真感光体をこの装置で28℃、90%RH下で通紙耐久(HH耐久)試験を行った。   The electrophotographic photosensitive member thus prepared was subjected to a paper passing durability test (HH durability) at 28 ° C. and 90% RH with this apparatus.

耐久試験は、1枚毎に1回停止する間欠モードとし、摩耗量の測定にはフィッシャー社製渦電流式膜厚測定機(パーマスコープ タイプ111)を用いた。   The durability test was an intermittent mode in which each sheet was stopped once, and an eddy current film thickness measuring machine (Permascope type 111) manufactured by Fischer was used for the measurement of the amount of wear.

トナーがなくなったならば補給し画像で問題がでるまで耐久した。また、研磨テープを用いたテーバー摩耗試験機を用い30分間摩耗させ、そのときの重量減少分を測定した。   If the toner runs out, it is replenished and it lasts until there is a problem with the image. Moreover, it was abraded for 30 minutes using a Taber abrasion tester using an abrasive tape, and the weight loss at that time was measured.

更に、電子写真感光体の一部に2000Luxで30分間、白色蛍光灯の光を照射し、5分間放置後、明部電位を測定し光を照射する前から明部電位がどれだけ下がったかを測定しフォトメモリー値とした。   Furthermore, a part of the electrophotographic photosensitive member is irradiated with light from a white fluorescent lamp at 2000 Lux for 30 minutes, and after being left for 5 minutes, the light portion potential is measured and how much the light portion potential has dropped before the light is irradiated. Measured and used as a photo memory value.

更に、ソルベントクラック性は、感光体表面に皮脂を付着させ72時間放置し、顕微鏡観察によりソルベントクラックの有無を観察し、クラックの認められたものを×、認められなかったものを○とした。   Further, for the solvent cracking property, sebum was attached to the surface of the photoreceptor and allowed to stand for 72 hours, and the presence or absence of the solvent crack was observed by microscopic observation.

その結果を表3に示す。   The results are shown in Table 3.

Figure 0003953072
分子量はゲルパーミエーションクロマトグラフィーで測定した。
Figure 0003953072
The molecular weight was measured by gel permeation chromatography.

(実施例2〜3)
電荷輸送層のバインダーに表1の樹脂No.2から3のものを用いた以外は、実施例1と同様にして電子写真感光体を作成し、評価した。その結果を表3に示す。
(Examples 2-3)
Resin No. 1 in Table 1 was used as the binder for the charge transport layer. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 2 to 3 were used. The results are shown in Table 3.

(比較例1〜4)
表2に示した条件1〜4の樹脂を用いた以外は、実施例1と同様にして電子写真感光体を作成し、評価した。その結果を表3に示す。
(Comparative Examples 1-4)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the resins of Conditions 1 to 4 shown in Table 2 were used. The results are shown in Table 3.

Figure 0003953072
Figure 0003953072

Figure 0003953072
条件1及び5のカルボン酸成分は、テレフタル酸/イソフタル酸をモル比で1/1とした。
Figure 0003953072
The carboxylic acid component under conditions 1 and 5 was terephthalic acid / isophthalic acid in a molar ratio of 1/1.

以上の結果から、本発明の電子写真感光体は、耐ソルベントクラック性に優れ、かつ良好な耐久特性を示すものであることが明らかとなった。   From the above results, it was clarified that the electrophotographic photosensitive member of the present invention has excellent solvent crack resistance and good durability characteristics.

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

Claims (4)

支持体及び感光層を有する電子写真感光体において、該電子写真感光体の表面層が、下記式(3)で示される繰り返し単位を有するポリエステル樹脂を含有することを特徴とする電子写真感光体。
Figure 0003953072
(式(3)中、Arは置換基を有しても良いアルキレン基を示し、RからR12は水素原子、ハロゲン原子または置換基を有しても良いアルキル基を示す。)
An electrophotographic photosensitive member having a support and a photosensitive layer, wherein the surface layer of the electrophotographic photosensitive member contains a polyester resin having a repeating unit represented by the following formula (3).
Figure 0003953072
(In formula (3), Ar 2 represents an alkylene group which may have a substituent, and R 9 to R 12 represent a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.)
前記ポリエステル樹脂が、前記式(3)で示される繰り返し単位と下記式(4)で示される繰り返し単位とを有する共重合体である請求項1に記載の電子写真感光体。
Figure 0003953072
(式(4)中、Arは置換されても良いアルキレン基を示す。)
The electrophotographic photoreceptor according to claim 1, wherein the polyester resin is a copolymer having a repeating unit represented by the formula (3) and a repeating unit represented by the following formula (4).
Figure 0003953072
(In formula (4), Ar 3 represents an optionally substituted alkylene group.)
請求項1または2に記載の電子写真感光体と、帯電手段、現像手段及びクリーニング手段からなる群より選ばれた少なくともひとつの手段とを一体に支持し、電子写真装置本体に着脱自在であることを特徴とするプロセスカートリッジ。   The electrophotographic photosensitive member according to claim 1 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 detachable from the main body of the electrophotographic apparatus. Process cartridge characterized by. 請求項1または2に記載の電子写真感光体、帯電手段、露光手段、現像手段及び転写手段を有することを特徴とする電子写真装置。   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.
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