JPH0625868B2 - Electrophotographic photoreceptor for positive charging - Google Patents
Electrophotographic photoreceptor for positive chargingInfo
- Publication number
- JPH0625868B2 JPH0625868B2 JP19588186A JP19588186A JPH0625868B2 JP H0625868 B2 JPH0625868 B2 JP H0625868B2 JP 19588186 A JP19588186 A JP 19588186A JP 19588186 A JP19588186 A JP 19588186A JP H0625868 B2 JPH0625868 B2 JP H0625868B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- resin
- charge
- pigments
- photoreceptor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0503—Inert supplements
- G03G5/051—Organic non-macromolecular compounds
- G03G5/0517—Organic non-macromolecular compounds comprising one or more cyclic groups consisting of carbon-atoms only
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
- G03G5/047—Photoconductive layers characterised by having two or more layers or characterised by their composite structure characterised by the charge-generation layers or charge transport layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/062—Acyclic or carbocyclic compounds containing non-metal elements other than hydrogen, halogen, oxygen or nitrogen
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電子写真感光体に関し、特に正帯電用感光体に
関する。The present invention relates to an electrophotographic photoreceptor, and more particularly to a positive charging photoreceptor.
従来、例えば電子写真感光体としては、セレン、酸化亜
鉛、硫化カドミウム等の無機光導電性物質を含有する感
光層を有する感光体が広く用いられている。Conventionally, for example, as an electrophotographic photoreceptor, a photoreceptor having a photosensitive layer containing an inorganic photoconductive substance such as selenium, zinc oxide, and cadmium sulfide has been widely used.
一方、種々の有機光導電性物質を電子写真感光体の感光
層の材料として利用することが近年活発に開発、研究さ
れている。On the other hand, the use of various organic photoconductive materials as materials for the photosensitive layer of an electrophotographic photoreceptor has been actively developed and studied in recent years.
例えば特公昭50-10496号公報には、ポリ−Ｎ−ビニルカ
ルバゾールと2,4,7,−トリニトロ−９−フルオレノンを
含有した感光層を有する有機感光体について記載されて
いる。しかしこの感光体は、感度及び耐久性において必
ずしも満足できるものではない。このような欠点を改善
するために、感光層において、電荷発生機能と電荷輸送
機能とを異なる物質に個別に分担させることにより、感
度が高くて耐久性の大きい有機感光体を開発する試みが
なされている。For example, JP-B-50-10496 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7, -trinitro-9-fluorenone. However, this photoreceptor is not always satisfactory in sensitivity and durability. In order to improve such a defect, an attempt has been made to develop an organic photoreceptor having high sensitivity and high durability by separately sharing a charge generating function and a charge transporting function with different substances in a photosensitive layer. ing.
このような、いわば機能分離型の電子写真感光体におい
ては、各機能を発揮する物質を広い範囲のものから選択
することができるので、任意の特性を有する電子写真感
光体を比較的容易に作製することが可能である。In such a so-called function-separated type electrophotographic photoconductor, since substances exhibiting respective functions can be selected from a wide range of substances, an electrophotographic photoconductor having arbitrary characteristics can be prepared relatively easily. It is possible to
こうした機能分離型の電子写真感光体に有効な電荷発生
物質として、従来数多くの物質が提案されている。無機
物質を用いる例としては、例えば特公昭43-16198号公報
に記載されているように、無定形セレンがあり、これは
有機電荷輸送物質と組み合わせる。Many substances have been proposed as charge generating substances effective for such a function-separated type electrophotographic photoreceptor. An example of using an inorganic substance is amorphous selenium, which is combined with an organic charge transport substance, as described in, for example, Japanese Patent Publication No. 43-16198.
また、有機染料や有機顔料を電荷発生物質として用いた
電子写真感光体も多数提案されており、例えば、ビスア
ゾ化合物を含有する感光層を有するものは、特開昭47-3
7543号、同55-22834号、同54-79632号、同56-116040号
各公報等により既に知られている。A number of electrophotographic photoreceptors using organic dyes and organic pigments as charge generating substances have also been proposed. For example, one having a photosensitive layer containing a bisazo compound is disclosed in JP-A-47-3.
It is already known from 7543, 55-22834, 54-79632, 56-116040, etc.
ところで、前記有機光導電性物質を用いた従来の感光体
は通常、負帯電用として使用されている。By the way, the conventional photoconductor using the organic photoconductive substance is usually used for negative charging.
この理由は、負帯電使用の場合には、電荷のうちホール
の移動度が大きいことから、光感度等の面で有利なため
である。しかしながら、このような負帯電使用では、次
の如き問題があることが判明している。即ち、帯電器に
よる負帯電時に雰囲気中にオゾンが発生し易くなり、環
境条件を悪くするという問題がある。さらに他の問題
は、負帯電用感光体の現像には正極性のトナーが必要と
なるが、正極性のトナーは強磁性体電荷粒子に対する摩
擦帯電系列からみて製造が困難であることである。The reason for this is that when negative charging is used, the mobility of holes in the charge is large, which is advantageous in terms of photosensitivity and the like. However, it has been found that the use of such negative charging has the following problems. That is, there is a problem that ozone is likely to be generated in the atmosphere during negative charging by the charger, which deteriorates environmental conditions. Still another problem is that a positive polarity toner is required for developing the negative charging photoreceptor, but the positive polarity toner is difficult to manufacture in view of the triboelectric charging series for the ferromagnetic particles.
そこで、有機光導電性物質を用いる感光体を正帯電で使
用することが提案されている。例えば、電荷発生層上に
電荷輸送層を積層して感光体を形成する際、感光体表面
の正電荷を能率よく打消すため前記電荷輸送層に電子輸
送能の大きい、例えばトリニトロフルオレノンを使用し
ているが、該物質は発ガン性があり、公害上極めて不適
当である。Therefore, it has been proposed to use a photoconductor using an organic photoconductive substance with positive charging. For example, when a photoconductor is formed by laminating a charge transport layer on a charge generation layer, a high electron transport capability such as trinitrofluorenone is used for the charge transport layer in order to efficiently cancel positive charges on the photoconductor surface. However, the substance is carcinogenic and extremely unsuitable for pollution.
さらに正帯電用感光体として、米国特許第3615414号明
細書には、チアピリリウム塩（電荷発生物質）をポリカ
ーボネート（バインダー樹脂）と共晶錯体を形成するよ
うに含有させたものが示されている。しかしこの公知の
感光体では、メモリー現象が大きく、ゴーストも発生し
易いという欠点がある。又米国特許第3357989号明細書
にも、フタロシアニンを含有せしめた感光体が示されて
いるが、フタロシアニンは結晶型によって特性が変化す
る上に、結晶型を厳密に制御しなければならないという
弊害があり、かつメモリー現象が大きく、短波長感度が
低いため前記短波長を含む可視光を光源とする複写機に
は不適当なものとされる。Further, as a positive charging photoreceptor, U.S. Pat. No. 3,615,414 discloses a thiapyrylium salt (charge-generating substance) contained in a eutectic complex with a polycarbonate (binder resin). However, this known photoconductor has a drawback that a memory phenomenon is large and a ghost is easily generated. Further, US Pat. No. 3357989 also shows a photoconductor containing phthalocyanine.However, phthalocyanine has the disadvantage that the characteristics change depending on the crystal type and that the crystal type must be strictly controlled. However, the memory phenomenon is large, and the short wavelength sensitivity is low, so that it is unsuitable for a copying machine using a visible light including the short wavelength as a light source.
このように正帯電用感光体を得るための試みが種々行な
われているが、いずれも光感度、メモリー又は公害等の
点で改善すべき多くの問題点がある。Although various attempts have been made to obtain a photoconductor for positive charging as described above, there are many problems to be solved in terms of photosensitivity, memory, pollution and the like.
そこで光照射時ホール及び電子を発生する電荷発生物質
を含有する電荷発生層を上層（表面層）とし、ホール輸
送機能を有する電荷輸送物質を含む電荷輸送層を下層と
する積層構成の感光層を有する感光体を正帯電用として
使用することが考えられる。さらに又、前記電荷発生物
質と前記電荷輸送物質を含む単層構成の感光層を有する
感光体も正帯電用として使用可能と考えられる。なおか
かる正帯電用とされる感光体においては、構造中に例え
ば電子吸引性基を有する電荷発生物質を用いるようにす
れば、感光体表面の正電荷を打消すための電子の移動が
早くなり、高感度特性が得られることが考えられる。Therefore, a photosensitive layer having a laminated structure is used in which a charge generation layer containing a charge generation substance that generates holes and electrons upon light irradiation is used as an upper layer (surface layer), and a charge transport layer containing a charge transport substance having a hole transport function is used as a lower layer. It is conceivable to use the photoconductor that it has for positive charging. Furthermore, it is considered that a photoreceptor having a single-layered photosensitive layer containing the charge generating substance and the charge transporting substance can also be used for positive charging. In such a photoconductor for positive charging, if a charge generating substance having an electron-withdrawing group is used in the structure, the movement of electrons for canceling the positive charge on the surface of the photoconductor becomes faster. It is considered that high sensitivity characteristics can be obtained.
しかしながら、前記正帯電用感光体はいずれも電荷発生
物質を含む層が表面層として形成されるため、光照射、
コロナ放電、湿度、特に機械的摩擦等の外部作用に敏感
な電荷発生物質が前記表面層近傍に存在することとな
り、感光体の保存中及び像形成の過程で電子写真性能が
劣化し、画質が低下するようになる。However, in each of the positive charging photoreceptors, since a layer containing a charge generating substance is formed as a surface layer, light irradiation,
The presence of a charge-generating substance that is sensitive to external effects such as corona discharge, humidity, and mechanical friction in particular, will be present near the surface layer, and the electrophotographic performance will deteriorate during storage of the photoconductor and during image formation, resulting in poor image quality. Will start to decline.
従来の電荷輸送層を表面層とする負帯電用感光体におい
ては、前記各種の各部作用の影響は極めて少なく、むし
ろ前記電荷輸送層が下層の電荷発生層を保護する作用を
有している。In the conventional negative charging photoreceptor having the charge transport layer as the surface layer, the effects of the various parts described above are extremely small, and the charge transport layer has a function of protecting the lower charge generating layer.
これに反して正帯電用感光体の場合は表面層とされる電
荷発生物質を含む層が外部作用、特に現像及びクリーニ
ング等により機械的摩耗及び損傷をうけ、白ポチ、白筋
等の画像欠陥その他表面電位、感度、メモリー、残留電
位等の電子写真性能の劣化が生ずるようになる。On the other hand, in the case of a positive charging photoreceptor, the layer containing the charge generating substance, which is the surface layer, is subject to mechanical abrasion and damage due to external action, especially development and cleaning, and image defects such as white spots and white streaks. In addition, deterioration of electrophotographic performance such as surface potential, sensitivity, memory and residual potential will occur.
そこで、例えば絶縁性かつ透明な樹脂から成る薄い保護
層を設け、前記電荷発生物質を含む層を補強することが
考えられるが、光照射時発生する電荷が該保護層でブロ
ッキングされて光導電性が失なわれるという問題があ
る。Therefore, for example, a thin protective layer made of an insulative and transparent resin may be provided to reinforce the layer containing the charge-generating substance. However, the charge generated during light irradiation is blocked by the protective layer and photoconductive There is a problem that is lost.
また、表面層となる電荷発生層の膜厚を増すことにより
電荷発生層の耐摩耗性および耐傷性を高めることが考え
られるが、膜厚の増加が感度低下を招くという問題があ
る。Further, it is possible to increase the wear resistance and scratch resistance of the charge generation layer by increasing the film thickness of the charge generation layer which is the surface layer, but there is a problem that an increase in the film thickness causes a decrease in sensitivity.
従って本発明の目的は、有機光導電性物質を用いて正帯
電用として好適に構成され、耐傷性に優れ高感度で耐久
性があり、しかもオゾン酸化耐性にも勝る電子写真感光
体を提供することにある。Therefore, an object of the present invention is to provide an electrophotographic photoreceptor that is suitably configured for positive charging using an organic photoconductive material, has excellent scratch resistance, high sensitivity, durability, and is superior in ozone oxidation resistance. Especially.
本発明の目的は、導電性支持体上に電荷輸送層、電荷発
生層および必要に応じて保護層を順次積層した電子写真
感光体において、電荷発生層中に電荷輸送物質を含有
し、かつ電荷発生層中あるいは保護層中に下記一般式で
示される化合物を含有する正帯電用電子写真感光体によ
って達成される。An object of the present invention is to provide an electrophotographic photoreceptor in which a charge transport layer, a charge generating layer and, if necessary, a protective layer are sequentially laminated on a conductive support, wherein the charge generating layer contains a charge transporting substance, and This is achieved by a positive charging electrophotographic photoreceptor containing a compound represented by the following general formula in the generating layer or the protective layer.
一般式 式中、Ｒ1およびＲ3は各々、炭素原子数１〜18のアルキ
ル基を表し、Ｒ2およびＲ4は各々、炭素原子数１〜18の
アルキル基またはアルコキシ基を表す。General formula In the formula, R 1 and R 3 each represent an alkyl group having 1 to 18 carbon atoms, and R 2 and R 4 each represent an alkyl group or an alkoxy group having 1 to 18 carbon atoms.
従来の技術でも記述したように有機光導電性物質を用い
た正帯電用感光体においては、電荷発生層（以下、ＣＧ
Ｌと略すことがある）が表面層となるので耐傷性に欠
け、耐久性向上のためにはＣＧＬ膜厚を厚くする必要が
ある。しかしながら、膜厚を厚くすると感度低下を引き
起こす。この感度低下を抑制する手段としてＣＧＬ中へ
の電荷輸送物質（以下、ＣＴＭと略すことがある）添加
があるが、このＣＴＭは電荷発生物質（以下、ＣＧＭと
略すことがある）に比べオゾン酸化を受け易い構造を有
するので、オゾンにより容易に劣化され感光体の耐久性
が損われてしまう。As described in the prior art, in the positive charging photoreceptor using the organic photoconductive material, the charge generation layer (hereinafter, referred to as CG
(It may be abbreviated as L) becomes a surface layer and thus lacks scratch resistance, and it is necessary to increase the CGL film thickness in order to improve durability. However, increasing the film thickness causes a decrease in sensitivity. As a means for suppressing this decrease in sensitivity, there is the addition of a charge transport substance (hereinafter, sometimes abbreviated as CTM) into CGL, but this CTM is more likely to be oxidized by ozone than a charge generation substance (hereinafter sometimes abbreviated as CGM). Since it has a structure that is easily affected by ozone, it is easily deteriorated by ozone and the durability of the photoreceptor is impaired.
本発明者らは、オゾン劣化性の改良に関し鋭意検討の結
果、正帯電用感光体の表面層であるＣＧＬ中にジ（２−
ヒドロキシフェニル）スルフィド系化合物を含有させる
ことにより、上記劣化を著しく軽減できることを見い出
し本発明をなすに至った。As a result of earnest studies on improvement of ozone deterioration, the present inventors have found that di (2-
It was found that the above deterioration can be remarkably reduced by containing a hydroxyphenyl) sulfide compound, and the present invention has been completed.
作用効果の詳細は不明であるが、オゾンがＣＧＬ中のＣ
ＴＭを劣化するより前に本発明の化合物に作用し、それ
以上のオゾン酸化をガードすることによりＣＴＭが保護
されるものと考える。The details of the action and effect are unknown, but ozone is C in CGL.
It is believed that the CTM is protected by acting on the compounds of the invention prior to degrading the TM and guarding against further ozone oxidation.
本発明の化合物は自身の酸化によってＣＴＭのオゾン劣
化を防止するので、必要に応じてＣＧＬ上に保護層（以
下、ＯＣＬと略すことがある）を設けた感光体において
は、勿論ＯＣＬ中に添加されるが、ＣＧＬにも添加され
てよく、更にＣＴＭを主成分とする電荷輸送層（以下、
ＣＴＬと略すことがある）にも添加されてよい。Since the compound of the present invention prevents the ozone deterioration of CTM by its own oxidation, in a photoreceptor having a protective layer (hereinafter sometimes abbreviated as OCL) provided on CGL, if necessary, it is added to OCL. However, the charge transport layer containing CTM as a main component (hereinafter,
(Sometimes abbreviated as CTL).
以下本発明をより具体的に詳述する。The present invention will be described in more detail below.
前記一般式で示される化合物において、Ｒ1，Ｒ2，
Ｒ3，およびＲ4で表されるアルキル基は直鎖でも分岐で
もよく、例えばメチル基、エチル基、プロピル基、ｉ−
ブチル基、ｔ−ブチル基、ペンチル基、ｔ−ペンチル
基、オクチル基、ｔ−オクチル基、ドデシル基等を挙げ
ることができる。In the compound represented by the above general formula, R 1 , R 2 ,
The alkyl group represented by R 3 and R 4 may be linear or branched and includes, for example, a methyl group, an ethyl group, a propyl group, i-
Examples thereof include a butyl group, a t-butyl group, a pentyl group, a t-pentyl group, an octyl group, a t-octyl group and a dodecyl group.
Ｒ2およびＲ4で表されるアルコキシ基としては、具体的
にメトキシ基、エトキシ基、プロポキシ基、ブトキシ
基、ヘキシルオキシ基、オクチルオキシ基、ドデシルオ
キシ基等が挙げられる。Specific examples of the alkoxy group represented by R 2 and R 4 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group and a dodecyloxy group.
本発明に好ましく用いられる化合物の代表的具体例を以
下に示すが、これに限定されるものではない。Typical specific examples of the compounds preferably used in the present invention are shown below, but the invention is not limited thereto.
これらの化合物は、プラスチック、合成繊維、エラスト
マー、ワックス、油脂類などの酸化防止剤として入手で
きる市販品も含む。 These compounds also include commercial products available as antioxidants such as plastics, synthetic fibers, elastomers, waxes and fats and oils.
本発明の化合物の添加量は、ＣＧＬ中に用いられる場
合、ＣＧＬ中のＣＴＭに対して0.1〜100重量％、好まし
くは１〜50重量％、特に好ましくは５〜25重量％であ
る。また、ＯＣＬ中に用いられる場合、ＯＣＬ中のバイ
ンダー樹脂に対して0.1〜100重量％、好ましくは１〜50
重量％である。When used in CGL, the amount of the compound of the present invention added is 0.1 to 100% by weight, preferably 1 to 50% by weight, particularly preferably 5 to 25% by weight, based on CTM in CGL. When used in OCL, it is 0.1 to 100% by weight, preferably 1 to 50% by weight based on the binder resin in OCL.
% By weight.
次に本発明の感光体の構成を図面によって説明する。感
光体としては例えば第１図に示すように支持体１（導電
性支持体またはシート上に導電層を設けたもの）上にＣ
ＴＭと必要に応じてバインダー樹脂を含有する電荷輸送
層２を下層とし、ＣＧＭ、ＣＴＭと必要に応じてバイン
ダー樹脂を含有する電荷発生層３を上層とする積層構成
の感光層４を設けたもの、第２図に示すように第１図の
感光層の上に保護層（ＯＣＬ）４を設けたもの、等が挙
げられるが、支持体と感光層の間に中間層が設けられて
もよい。Next, the structure of the photoconductor of the present invention will be described with reference to the drawings. As a photoconductor, for example, as shown in FIG. 1, C on a support 1 (a conductive support or a sheet on which a conductive layer is provided) is used.
A photosensitive layer 4 having a laminated structure in which a charge transport layer 2 containing TM and a binder resin as necessary is used as a lower layer, and a charge generation layer 3 containing CGM and CTM and a binder resin as needed is used as an upper layer. 2, a protective layer (OCL) 4 is provided on the photosensitive layer shown in FIG. 1, and the like, but an intermediate layer may be provided between the support and the photosensitive layer. .
次に本発明に適する電荷発生物質としては、可視光を吸
収してフリー電荷を発生するものであれば、無機顔料及
び有機色素の何れをも用いることができる。無定形セレ
ン、三方晶系セレン、セレン−砒素合金、セレン−テル
ル合金、硫化カドミウム、セレン化カドミウム、硫セレ
ン化カドミウム、硫化水銀、酸化鉛、硫化鉛等の無機顔
料の外、次の代表例で示されるような有機顔料を用いて
もよい。Next, as the charge generating substance suitable for the present invention, any of inorganic pigments and organic dyes can be used as long as they absorb visible light and generate free charges. In addition to inorganic pigments such as amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium sulphide selenide, mercury sulfide, lead oxide, lead sulfide, the following typical examples You may use the organic pigment shown by.
（１）モノアゾ顔料、ポリアゾ顔料、金属錯塩アゾ顔
料、ピラゾロンアゾ顔料、スチルベンアゾ及びチアゾー
ルアゾ顔料等のアゾ系顔料。(1) Azo pigments such as monoazo pigments, polyazo pigments, metal complex salt azo pigments, pyrazolone azo pigments, stilbene azo and thiazole azo pigments.
（２）ペリレン酸無水物及びペリレン酸イミド等のペリ
レン系顔料。(2) Perylene pigments such as perylene anhydride and perylene imide.
（３）アントラキノン誘導体、アントアントロン誘導
体、ジベンズピレンキノン誘導体、ピラントロン誘導
体、ビオラントロン誘導体及びイソビオラントロン誘導
体等のアントラキノン系又は多環キノン系顔料 （４）インジゴ誘導体及びチオインジゴ誘導体等のイン
ジゴイド系顔料 （５）金属フタロシアニン及び無金属フタロシアニン等
のフタロシアニン系顔料 （６）ジフェニルメタン系顔料、トリフェニルメタン顔
料、キサンテン顔料及びアクリジン顔料等のカルボニウ
ム系顔料 （７）アジン顔料、オキサジン顔料及びチアジン顔料等
のキノンイミン系顔料 （８）シアニン顔料及びアゾメチン顔料等のメチン系顔
料 （９）キノリン系顔料 (10)ニトロ系顔料 (11)ニトロソ系顔料 (12)ベンゾキノン及びナフトキノン系顔料 (13)ナフタルイミド系顔料 (14)ビスベンズイミダゾール誘導体等のペリノン系顔料 電子吸引性基を有する種々のアゾ顔料が、感度、メモリ
ー現象、残留電位等の電子写真特性の良好さから用いら
れるが耐オゾン性の点で多環キノン系顔料が最も好まし
い。(3) Anthraquinone-based or polycyclic quinone-based pigments such as anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives and isobiolanthrone derivatives (4) Indigoide pigments such as indigo derivatives and thioindigo derivatives (5) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine (6) Carbonium pigments such as diphenylmethane pigments, triphenylmethane pigments, xanthene pigments and acridine pigments (7) Quinoneimines such as azine pigments, oxazine pigments and thiazine pigments Pigments (8) Methine pigments such as cyanine pigments and azomethine pigments (9) Quinoline pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and naphthoquinone pigments (13) Naphthalimide Pigment (14) Perinone-based pigments such as bisbenzimidazole derivatives Various azo pigments having an electron-withdrawing group are used because of good electrophotographic characteristics such as sensitivity, memory phenomenon and residual potential, but in terms of ozone resistance. Most preferred are polycyclic quinone pigments.
詳細は不明であるが、おそらくアゾ基はオゾン酸化を受
け易く電子写真特性が低下してしまうが、多環キノン類
はオゾンに対して不活性であるためと思われる。Although the details are unknown, it is presumed that the azo group is susceptible to ozone oxidation and the electrophotographic properties deteriorate, but the polycyclic quinones are inactive to ozone.
前記本発明に用いられるアゾ系顔料としては、例えば次
の例示化合物群〔Ｉ〕〜〔Ｖ〕で示されるものがある。Examples of the azo pigments used in the present invention include those shown in the following exemplary compound groups [I] to [V].
また、以下の多環キノン顔料から成る例示化合物群〔V
I〕〜〔VIII〕はＣＧＭとして最も好ましく使用でき
る。 In addition, an exemplary compound group consisting of the following polycyclic quinone pigments [V
I] to [VIII] can be most preferably used as CGM.
次に本発明で使用可能な電荷輸送物質としては、特に制
限はないが、例えばオキサゾール誘導体、オキサジアゾ
ール誘導体、チアゾール誘導体、チアジアゾール誘導
体、トリアゾール誘導体、イミダゾール誘導体、イミダ
ゾロン誘導体、イミダゾリジン誘導体、ビスイミダゾリ
ジン誘導体、スチリル化合物、ヒドラゾン化合物、ピラ
ゾリン誘導体、オキサゾロン誘導体、ベンゾチアゾール
誘導体、ベンズイミダゾール誘導体、キナゾリン誘導
体、ベンゾフラン誘導体、アクリジン誘導体、フエナジ
ン誘導体、アミノスチルベン誘導体、ポリ−Ｎ−ビニル
カルバゾール、ポリ−１−ビニルピレン、ポリ−９−ビ
ニルアントラセン等であってよい。 Next, the charge-transporting substance that can be used in the present invention is not particularly limited, and examples thereof include an oxazole derivative, an oxadiazole derivative, a thiazole derivative, a thiadiazole derivative, a triazole derivative, an imidazole derivative, an imidazolone derivative, an imidazolidine derivative, and a bisimidazole. Lysine derivative, styryl compound, hydrazone compound, pyrazoline derivative, oxazolone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, poly-N-vinylcarbazole, poly-1- It may be vinylpyrene, poly-9-vinylanthracene and the like.
しかしながら光照射時発生するホールの支持体側への輸
送能力が優れている外、前記キャリア発生物質との組合
せに好適なものが好ましく用いられ、かかるＣＴＭとし
ては、例えば下記例示化合物群〔IX〕又は〔Ｘ〕で示さ
れるスチル化合物が使用される。However, in addition to the excellent ability of transporting holes generated upon light irradiation to the support side, those suitable for combination with the carrier generating substance are preferably used. Examples of such CTM include the following exemplified compound group [IX] or The still compound represented by [X] is used.
また、ＣＴＭとして下記例示化合物群〔XI〕〜〔XV〕で
示されるヒドラゾン化合物も使用可能である。 In addition, hydrazone compounds represented by the following exemplified compound groups [XI] to [XV] can also be used as CTM.
また、ＣＴＭとして下記例示化合物〔XVI〕で示される
ピラゾリン化合物も使用可能である。 Further, a pyrazoline compound represented by the following exemplified compound [XVI] can also be used as the CTM.
また、ＣＴＭとして下記例示化合物群〔XVII〕で示され
るアミン誘導体も使用可能である。 Further, amine derivatives represented by the following exemplified compound group [XVII] can also be used as CTM.
次に本発明に用いられてよい保護層はバインダーとして
体積抵抗108Ω・cm以上、好ましくは1010Ω・cm以上、
より好ましくは1013Ω・cm以上の透明樹脂が用いられ
る。又前記バインダーは光又は熱により硬化する樹脂を
少なくとも50重量％以上含有するものとされる。 Next, the protective layer which may be used in the present invention has a volume resistance of 10 8 Ωcm or more as a binder, preferably 10 10 Ωcm or more,
More preferably, a transparent resin of 10 13 Ω · cm or more is used. The binder contains at least 50% by weight of a resin that is cured by light or heat.
かかる光又は熱により硬化する樹脂としては、例えば熱
硬化性アクリル樹脂、シリコン樹脂、エポキシ樹脂、ウ
レタン樹脂、尿素樹脂、フェノール樹脂、ポリエステル
樹脂、アルキッド樹脂、メラミン樹脂、光硬化性・桂皮
酸樹脂等又はこれらの共重合もしくは共縮合樹脂があ
り、その外電子写真材料に供される光又は熱硬化性樹脂
の全てが利用される。又前記保護層中には加工性及び物
性の改良（亀裂防止、柔軟性付与等）を目的として必要
により熱可塑性樹脂を50重量％未満含有せしめることが
できる。かかる熱可塑性樹脂としては、例えばポリプロ
ピレン、アクリル樹脂、メタクリル樹脂、塩化ビニル樹
脂、酢酸ビニル樹脂、エポキシ樹脂、ブチラール樹脂、
ポリカーボネート樹脂、シリコン樹脂、又はこれらの共
重合樹脂、例えば塩化ビニル−酢酸ビニル共重合体樹
脂、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体
樹脂、ポリ−Ｎ−ビニルカルバゾール等の高分子有機半
導体、その他電子写真材料に供される熱可塑性樹脂の全
てが利用される。Examples of the resin that is cured by light or heat include thermosetting acrylic resin, silicone resin, epoxy resin, urethane resin, urea resin, phenol resin, polyester resin, alkyd resin, melamine resin, and photocurable cinnamic acid resin. Alternatively, there are copolymerization or co-condensation resins of these, and all of the photo- or thermosetting resins provided for the electrophotographic material can be used. If necessary, the protective layer may contain less than 50% by weight of a thermoplastic resin for the purpose of improving workability and physical properties (preventing cracks, imparting flexibility, etc.). Examples of such thermoplastic resin include polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, butyral resin,
Polycarbonate resin, silicone resin, or copolymer resin thereof, for example, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, polymer organic semiconductor such as poly-N-vinylcarbazole , And all other thermoplastic resins used for electrophotographic materials are used.
また前記保護層は、電子受容性物質を含有してもよく、
その他、必要によりＣＧＭを保護する目的で紫外線吸収
剤等を含有してもよく、前記バインダーと共に溶剤に溶
解され、例えばディップ塗布、スプレー塗布、ブレード
塗布、ロール塗布等により塗布・乾燥されて２μｍ以
下、好ましくは１μｍ以下の層厚に形成される。Further, the protective layer may contain an electron accepting substance,
In addition, if necessary, an ultraviolet absorber or the like may be contained for the purpose of protecting the CGM, and it is dissolved in a solvent together with the binder and coated / dried by, for example, dip coating, spray coating, blade coating, roll coating, etc. It is preferably formed to a layer thickness of 1 μm or less.
本発明の感光体の感光層の層構成は前記のように、積層
構成であるが、電荷輸送層、電荷発生層または保護層に
は感度の向上、残留電位ないし反復使用時の疲労低減等
を目的として、１種または２種以上の電子受容性物質を
含有せしめることができる。Although the layer structure of the photosensitive layer of the photoreceptor of the present invention is a laminated structure as described above, the charge transport layer, the charge generation layer or the protective layer has improved sensitivity, residual potential or reduced fatigue during repeated use. For the purpose, one kind or two or more kinds of electron accepting substances may be contained.
本発明に使用可能な電子受容性物質としては、例えば無
水コハク酸、無水マレイン酸、ジブロム無水マレイン
酸、無水フタル酸、テトラクロル無水フタル酸、テトラ
ブロム無水フタル酸、３−ニトロ無水フタル酸、４−ニ
トロ無水フタル酸、無水ピロメリット酸、無水メリット
酸、テトラシアノエチレン、テトラシアノキノジメタ
ン、ｏ−ジニトロベンゼン、ｍ−ジニトロベンゼン、
１，３，５，−トリニトロベンゼン、パラニトロベンゾ
ニトリル、ピクリルクロライド、キノンクロルイミド、
クロラニル、ブルマニル、２−メチルナフトキノン、ジ
クロロジシアノパラベンゾキノン、アントラキノン、ジ
ニトロアントラキノン、トリニトロフルオレノン、９−
フルオレニリデン〔ジシアノメチレンマロノジニトリ
ル〕、ポリニトロ−９−フルオレニリデン−〔ジシアノ
メチレンマロノジニトリル〕、ピクリン酸、ｏ−ニトロ
安息香酸、ｐ−ニトロ安息香酸、３，５−ジニトロ安息
香酸、ペンタフルオロ安息香酸、５−ニトロサリチル
酸、３，５−ジニトロサリチル酸、フタル酸等が挙げら
れる。Examples of the electron accepting substance that can be used in the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4- Nitrophthalic anhydride, pyromellitic dianhydride, mellitic dianhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene,
1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide,
Chloranil, bulmannyl, 2-methylnaphthoquinone, dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, trinitrofluorenone, 9-
Fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9-fluorenylidene- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid , 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid and the like.
本発明において感光層に使用可能なバインダー樹脂とし
ては、例えばポリエチレン、ポリプロピレン、アクリル
樹脂、メタクリル樹脂、塩化ビニル樹脂、酢酸ビニル樹
脂、エポキシ樹脂、ポリウレタン樹脂、フェノール樹
脂、ポリエステル樹脂、アルキッド樹脂、ポリカーボネ
ート樹脂、シリコン樹脂、メラミン樹脂等の付加重合型
樹脂、重付加型樹脂、重縮合型樹脂、並びにこれらの樹
脂の繰り返し単位のうちの２つ以上を含む共重合体樹
脂、例えば塩化ビニル−酢酸ビニル共重合体樹脂、塩化
ビニル−酢酸ビニル−無水マレイン酸共重合体樹脂等の
絶縁性樹脂の他、ポリ−Ｎ−ビニルカルバゾール等の高
分子有機半導体が挙げられる。Examples of the binder resin usable in the photosensitive layer in the present invention include polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, and polycarbonate resin. , Addition resins such as silicone resins and melamine resins, polyaddition resins, polycondensation resins, and copolymer resins containing two or more of the repeating units of these resins, for example vinyl chloride-vinyl acetate copolymers. In addition to insulating resins such as polymer resins and vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, polymer organic semiconductors such as poly-N-vinylcarbazole may be mentioned.
次に前記感光層を支持する導電性支持体としては、アル
ミニウム、ニッケルなどの金属板、金属ドラム又は金属
箔、アルミニウム、酸化スズ、酸化インジウムなどを蒸
着したプラスチックフイルムあるいは導電性物質を塗布
した紙、プラスチックなどのフイルム又はドラムを使用
することができる。Next, as a conductive support for supporting the photosensitive layer, a metal plate such as aluminum or nickel, a metal drum or a metal foil, a plastic film deposited with aluminum, tin oxide, indium oxide or the like or a paper coated with a conductive substance A film or drum made of plastic, etc. can be used.
電荷輸送層は既述のＣＴＭを適当な溶媒に単独もしくは
適当なバインダー樹脂と共に溶解もしくは分散せしめた
ものを塗布して乾燥させる方法により設ける。The charge transport layer is provided by a method in which the above-mentioned CTM is dissolved or dispersed in a suitable solvent alone or together with a suitable binder resin and then dried.
ＣＴＬの形成に用いられる溶媒としては、例えばN,N−
ジメチルホルムアミド、ベンゼン、トルエン、キシレ
ン、モノクロルベンゼン、１，２−ジクロロエタン、ジ
クロロメタン、1,1,2−トリクロロエタン、テトラヒド
ロフラン、メチルエチルケトン、酢酸エチル、酢酸ブチ
ル等を挙げることができる。Examples of the solvent used for forming CTL include N, N-
Examples thereof include dimethylformamide, benzene, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, dichloromethane, 1,1,2-trichloroethane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate and butyl acetate.
形成されるＣＴＬの膜厚は、好ましくは５〜50μｍ、特
に好ましくは５〜30μｍである。The thickness of the formed CTL is preferably 5 to 50 μm, particularly preferably 5 to 30 μm.
ＣＴＬ中のバインダー樹脂100重量部当りＣＴＭが20〜2
00重量部、好ましくは30〜150重量部とされる。CTM of 20 to 2 per 100 parts by weight of binder resin in CTL
The amount is 00 parts by weight, preferably 30 to 150 parts by weight.
ＣＴＭの含有割合がこれより少ないと光感度が悪く、残
留電位が高くなり易く、これより多いと溶媒溶解性が悪
くなる。If the content ratio of CTM is less than this range, the photosensitivity is poor and the residual potential tends to be high, and if it is more than this range, the solvent solubility is poor.
電荷発生層は、既述のＣＧＭとＣＴＭを別々に、あるい
は一緒に適当な溶剤に単独もしくは適当なバインダー樹
脂と共に溶解もしくは分散せしめたものを塗布、乾燥し
てＣＴＬの場合と同様に形成することができる。The charge generation layer should be formed in the same manner as in the case of CTL by coating the above CGM and CTM separately or together or dissolving or dispersing them in a suitable solvent alone or with a suitable binder resin and drying. You can
上記ＣＧＭを分散せしめてＣＧＬを形成する場合、当該
ＣＧＭは２μｍ以下、好ましくは１μｍ以下の平均粒径
の粉粒体とされるのが好ましい。即ち、粒径があまり大
きいと層中への分散が悪くなると共に、粒子が表面に一
部突出して表面の平滑性が悪くなり、場合によっては粒
子の突出部分で放電が生じたり或いはそこにトナー粒子
が付着してトナーフィルミング現象が生じ易い。When forming the CGL by dispersing the CGM, the CGM is preferably a powder or granule having an average particle size of 2 μm or less, preferably 1 μm or less. That is, if the particle size is too large, the dispersion in the layer becomes poor, and the particles partially project on the surface to deteriorate the smoothness of the surface. Toner filming phenomenon is likely to occur due to particles attached.
ただし、上記粒径があまり小さいと却って凝集し易く、
層の抵抗が上昇したり、結晶欠陥が増えて感度及び繰返
し特性が低下したり、或いは微細化する上で限界がある
から、平均粒径の下限を0.01μｍとするのが望ましい。However, if the above particle size is too small, it tends to aggregate,
It is desirable to set the lower limit of the average grain size to 0.01 μm, because the resistance of the layer increases, the crystal defects increase and the sensitivity and repeatability deteriorate, or there is a limit in miniaturization.
ＣＧＬは、次の如き方法によって設けることができる。
即ち、記述のＣＧＭをボールミル、ホモミキサー等によ
って分散媒中で微細粒子として、バインダー樹脂および
ＣＴＭを加えて混合分散して得られる分散液を塗布する
方法である。この方法において超音波の作用下に粒子を
分散させると、均一分散が可能である。The CGL can be provided by the following method.
That is, it is a method of applying the dispersion liquid obtained by finely mixing the described CGM in a dispersion medium by a ball mill, a homomixer or the like, adding a binder resin and CTM, mixing and dispersing them. In this method, if the particles are dispersed under the action of ultrasonic waves, uniform dispersion is possible.
ＣＧＬ中のバインダー樹脂100重量当りＣＧＭが20〜200
重量部、好ましくは25〜100重量部とされ、ＣＴＭが20
〜200重量部、好ましくは30〜150重量部とされる。20 to 200 CGM per 100 weight of binder resin in CGL
Parts by weight, preferably 25-100 parts by weight, with a CTM of 20
˜200 parts by weight, preferably 30 to 150 parts by weight.
ＣＧＭがこれより少ないと光感度が低く、残留電位の増
加を招き、又これより多いと暗減衰が増大し、かつ受容
電位が低下する。If the CGM is less than this, the photosensitivity is low and the residual potential is increased, and if it is more than this, the dark decay is increased and the receptive potential is lowered.
以上のようにして形成されるＣＧＬの膜厚は、好ましく
は１〜10μｍ、特に好ましくは２〜７μｍである。The film thickness of the CGL formed as described above is preferably 1 to 10 μm, particularly preferably 2 to 7 μm.
ＣＧＬとＣＴＬの膜厚比は１：（１〜30）であるのが好
ましい。The film thickness ratio of CGL and CTL is preferably 1: (1-30).
以下本発明を実施例により説明するが、これにより本発
明の実施の態様が限定されるものではない。The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereby.
実施例１ アルミニウム箔をラミネートしたポリエステルフイルム
より成る導電性支持体上に、塩化ビニル−酢酸ビニル−
無水マレイン酸共重合体（エスレックＭＦ−10、積水化
学工業社製）よりなる厚さ0.1μｍの中間層を形成し
た。Example 1 Vinyl chloride-vinyl acetate-on a conductive support made of a polyester film laminated with aluminum foil.
A 0.1 μm thick intermediate layer made of a maleic anhydride copolymer (S-REC MF-10, manufactured by Sekisui Chemical Co., Ltd.) was formed.
次いでポリカーボネート樹脂（パンライトＬ−1250帝人
化成社製）／ＣＴＭ（IX-75）＝100/75（重量比）を16.
5重量％含有する1,2−ジクロルエタン溶液を中間層上に
ディップ塗布し、15μｍ厚の電荷輸送層を形成した。次
に、ＣＧＭとして昇華した4,10−ジブロムアンスアンス
ロン（VI-3）／パンライトＬ−1250＝1/2（重量比）が
９重量％になるように1,2−ジクロルエタン中ボールミ
ルで24時間粉砕し、更に24時間分散した液にＣＴＭ（IX
-75）をパンライトＬ−1250に対して75重量％およびＣ
ＴＭに対して10重量％の例示化合物(4)を加えた。この
溶液にモノクロルベンゼンを加えて1,2−ジクロルベン
ゼン／モノクロルベンゼン＝7/3（体積比）になるよう
調製した分散液を前記ＣＴＬ上にスプレー塗布し、乾燥
して５μｍの電荷発生層を形成し、積層構成の感光層を
有する本発明に係る感光体を得た。Then polycarbonate resin (Panlite L-1250, Teijin Chemicals Co., Ltd.) / CTM (IX-75) = 100/75 (weight ratio) 16.
A 1,2-dichloroethane solution containing 5% by weight was dip-coated on the intermediate layer to form a charge transport layer having a thickness of 15 μm. Then, in a ball mill in 1,2-dichloroethane so that 4,10-dibromoanthanthrone (VI-3) / Panlite L-1250 = 1/2 (weight ratio) sublimated as CGM is 9% by weight. CTM (IX
-75) to 75% by weight of Panlite L-1250 and C
10% by weight of the exemplified compound (4) was added to TM. A dispersion liquid prepared by adding monochlorobenzene to this solution so that 1,2-dichlorobenzene / monochlorobenzene = 7/3 (volume ratio) is spray-coated on the CTL and dried to give a charge generation layer of 5 μm. Was formed to obtain a photoreceptor according to the present invention having a photosensitive layer having a laminated structure.
比較例１ 実施例１において、例示化合物(4)を除いた以外は実施
例１と全く同様にして比較の感光体を得た。Comparative Example 1 A comparative photoreceptor was obtained in the same manner as in Example 1 except that the exemplified compound (4) was omitted.
実施例２ 実施例１において、例示化合物(4)に代えて例示化合物
(I)を用いた以外は全く同様にして感光体を得た。Example 2 The example compound in place of the example compound (4) in the example 1
A photoconductor was obtained in exactly the same manner except that (I) was used.
実施例３ 実施例１の例示化合物(4)を除いた感光層（比較例１の
感光体に同じ）上に、熱硬化性アクリル−メラミン−エ
ポキシ（１：１：１）樹脂1.55重量部および例示化合物
(4)0.155重量部をモノクロルベンゼン／1,1,2−トリク
ロルエタン混合溶媒に溶解させた塗布液をスプレー塗布
し、乾燥して１μｍ厚の保護層を有する感光体を得た。Example 3 1.55 parts by weight of a thermosetting acrylic-melamine-epoxy (1: 1: 1) resin on a photosensitive layer (same as the photoreceptor of Comparative Example 1) excluding the exemplified compound (4) of Example 1 and Exemplified compound
(4) 0.155 parts by weight of a coating solution prepared by dissolving 0.155 parts by weight of a monochlorobenzene / 1,2-trichloroethane mixed solvent was spray-coated and dried to obtain a photoreceptor having a protective layer with a thickness of 1 μm.
実施例４ 実施例１の例示化合物(4)を除いた感光層上に、シリコ
ンハードコート用プライマーPH91（東芝シリコン社製）
を0.1μｍとなるようにスプレー塗布し、更にその上に
シリコンハードコートトスガード510（東芝シリコン社
製）及び例示化合物(4)を樹脂100重量部に対して10重量
部となるよう添加した溶液をスプレー塗布し、乾燥して
１μｍ厚の保護層を形成し感光体を得た。Example 4 A silicon hard coat primer PH91 (manufactured by Toshiba Silicon Co., Ltd.) was formed on the photosensitive layer excluding the exemplified compound (4) of Example 1.
Was spray-coated to 0.1 μm, and silicon hard coat Tosguard 510 (manufactured by Toshiba Silicon Co., Ltd.) and Exemplified Compound (4) were added thereto in an amount of 10 parts by weight with respect to 100 parts by weight of the resin. Was spray-coated and dried to form a protective layer having a thickness of 1 μm to obtain a photoreceptor.
実施例５ アルミニウム箔をラミネートしたポリエステルフィルム
より成る導電性支持体上に、塩化ビニル−酢酸ビニル−
無水マレイン酸共重合体（エスレックＭＦ−10、前出）
よりなる厚さ約0.1μｍの中間層を形成した。Example 5 Vinyl chloride-vinyl acetate-on a conductive support made of a polyester film laminated with aluminum foil.
Maleic anhydride copolymer (S-REC MF-10, supra)
To form an intermediate layer having a thickness of about 0.1 μm.
次いでＣＴＬ用塗布液としてブチラール樹脂（エスレッ
クＢＸ−１、積水化学社製）８重量％とＣＴＭ（IX-7
5）６重量％をメチルエチルケトンに溶解して得られる
塗布液を前記中間層上に塗布・乾燥して10μｍ厚の電荷
輸送層を形成した。次いでＣＧＭ（IV−７）0.2ｇをペ
イントコンデショナー（Paint Conditioner、Red Devil
社製）で30分粉砕し、これにポリカーボネート樹脂（パ
ンライトＬ−1250、前出）を1,2−ジクロルエタン／1,
1,2−トリクロルエタン混合溶媒に0.5重量％となるよう
溶解させた溶液を8.3ｇ加えて３分間分散し、次いでこ
れにポリカーボネート樹脂、ＣＴＭ（IX-75）および例
示化合物(4)をそれぞれ3.3重量％、2.6重量％および0.2
6重量％となるよう1,2−ジクロルエタン／1,1,2−トリ
クロルエタン混合溶媒に溶解して得られる溶液19.1ｇを
加えてさらに30分間分散した。かくして得られた分散液
を前記ＣＴＬ上にスプレー塗布し、かつ乾燥して５μｍ
厚の電荷発生層を形成し、積層構成の感光層を有する感
光体を得た。Next, as a coating liquid for CTL, 8% by weight of butyral resin (S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and CTM (IX-7
5) A coating solution obtained by dissolving 6% by weight in methyl ethyl ketone was applied onto the intermediate layer and dried to form a charge transport layer having a thickness of 10 μm. Next, 0.2 g of CGM (IV-7) was added to Paint Conditioner, Red Devil.
(Manufactured by the company) for 30 minutes and add polycarbonate resin (Panlite L-1250, previously mentioned) to this, 1,2-dichloroethane / 1,
8.3 g of a solution prepared by dissolving 0.5% by weight of a 1,2-trichloroethane mixed solvent was added and dispersed for 3 minutes, and then a polycarbonate resin, CTM (IX-75) and Exemplified compound (4) were added to each of 3.3 parts. % By weight, 2.6% by weight and 0.2
19.1 g of a solution obtained by dissolving it in a 1,2-dichloroethane / 1,1,2-trichloroethane mixed solvent so as to be 6% by weight was added and dispersed for another 30 minutes. The dispersion thus obtained is spray-coated on the CTL and dried to 5 μm.
A thick charge generation layer was formed to obtain a photoreceptor having a laminated photosensitive layer.
比較例２ 実施例５において例示化合物(4)を除いた以外は実施例
５と全く同様にして比較の感光体を得た。Comparative Example 2 A comparative photoreceptor was obtained in exactly the same manner as in Example 5, except that the exemplified compound (4) was omitted.
実施例６ 実施例５において、例示化合物(4)に代えて例示化合物
(I)を用いた以外は全く同様にして感光体を得た。Example 6 The example compound in place of the example compound (4) in the example 5
A photoconductor was obtained in exactly the same manner except that (I) was used.
実施例７ 実施例５の例示化合物(4)を除いた感光層（比較例２の
感光体に同じ）上に、実施例３と同様の例示化合物(4)
を含有する保護層を設置し、感光体を得た。Example 7 The same exemplified compound (4) as in Example 3 was formed on the photosensitive layer (same as the photoreceptor of Comparative Example 2) except for the exemplified compound (4) of Example 5.
A protective layer containing was installed to obtain a photoreceptor.
実施例８ 実施例５の例示化合物(4)を除いた感光層上に、実施例
４と同様の例示化合物(4)を含有する保護層を設置し、
感光体を得た。Example 8 A protective layer containing the same exemplified compound (4) as in Example 4 was provided on the photosensitive layer except the exemplified compound (4) of Example 5,
A photoconductor was obtained.
上記のようにして得られた感光体試料を次に示すオゾン
疲労試験機により耐オゾン性を評価した。すなわち、静
電試験機（川口電気製作所製ＳＰ−428型）にオゾン発
生器（日本オゾン株式会社製０−１−２型）およびオゾ
ンモニター（エバラ実業株式会社製ＥＧ−2001型）を取
り付けた装置を用いた。オゾン濃度90ppmにおいて感光
体を装着し、＋６ＫＶの電圧を印加して５秒間のコロナ
放電により感光層を帯電させた後５秒間放置（この時の
電位を初期電位Ｖ0とする）し、次いで感光層表面の照
度が14ルックスとなる状態でタングステンランプよりの
光を照射し、この操作を100回くり返した。The photoreceptor samples obtained as described above were evaluated for ozone resistance by the ozone fatigue tester shown below. That is, an electrostatic tester (Kawaguchi Denki Seisakusho SP-428 type) was equipped with an ozone generator (Nihon Ozone Co., Ltd. 0-1-2 type) and an ozone monitor (Ebara Industrial Co., Ltd. EG-2001 type). The device was used. A photoreceptor was mounted at an ozone concentration of 90 ppm, a voltage of +6 KV was applied, and the photosensitive layer was charged by corona discharge for 5 seconds, and then left for 5 seconds (the potential at this time is defined as an initial potential V 0 ) and then exposed. The operation was repeated 100 times by irradiating light from a tungsten lamp while the illuminance on the layer surface was 14 lux.
100回照射後の電位をＶ1とする時、Ｖ1／Ｖ0×100％で
耐オゾン性を表した。Ｖ1／Ｖ0は100回反復後の電位低
下の程度を示すものであり、数値が大きい程好ましい。When the potential after 100 times of irradiation was V 1 , the ozone resistance was expressed as V 1 / V 0 × 100%. V 1 / V 0 indicates the degree of potential decrease after 100 times of repetition, and the larger the value, the better.
また、オゾンを導入しないで、初期電位を＋600Ｖから
＋100Ｖに減衰させるに必要な露光量▲Ｅ600 100▼（ル
ックス・秒）も測定した。数値が小さい程、感度が高い
ことを示す。これらの結果を別表に示す。Further, the exposure amount ▲ E 600 100 ▼ (lux seconds) required to attenuate the initial potential from +600 V to +100 V without introducing ozone was also measured. The smaller the value, the higher the sensitivity. These results are shown in the attached table.
別表から本発明の感光体はいずれも耐オゾン性および電
子写真特性共にすぐれているのに対し、比較用感光体は
オゾン劣化が著しく電子写真特性も良くないことが判
る。 It can be seen from the attached table that all of the photoconductors of the present invention are excellent in ozone resistance and electrophotographic properties, whereas the comparative photoconductor is markedly deteriorated by ozone and has poor electrophotographic properties.
第１図及び第２図は本発明の正帯電用感光体の断面図で
ある。 １…支持体 ２…電荷輸送層 ３…電荷発生層 ４…感光層 ５…電荷輸送物質（ＣＴＭ） ６…電荷発生物質（ＣＧＭ） ７…保護層1 and 2 are sectional views of the positive charging photoreceptor of the present invention. DESCRIPTION OF SYMBOLS 1 ... Support body 2 ... Charge transport layer 3 ... Charge generation layer 4 ... Photosensitive layer 5 ... Charge transport material (CTM) 6 ... Charge generation material (CGM) 7 ... Protective layer
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−14844（ＪＰ，Ａ) 特開 昭61−156131（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-14844 (JP, A) JP-A-61-156131 (JP, A)
Claims (1)
および必要に応じて保護層を順次積層した電子写真感光
体において、電荷発生層中に電荷輸送物質を含有し、か
つ電荷発生層中あるいは保護層中に下記一般式で示され
る化合物を含有することを特徴とする正帯電用電子写真
感光体。 一般式 〔式中、Ｒ1およびＲ3は各々、炭素原子数１〜18のアル
キル基を表し、Ｒ2およびＲ4は各々、炭素原子数１〜18
のアルキル基またはアルコキシ基を表す。〕1. An electrophotographic photosensitive member comprising a conductive support, and a charge transport layer, a charge generating layer and, if necessary, a protective layer, which are sequentially laminated, wherein the charge generating layer contains a charge transporting substance. An electrophotographic photoreceptor for positive charging, comprising a compound represented by the following general formula in a layer or a protective layer. General formula [In the formula, R 1 and R 3 each represent an alkyl group having 1 to 18 carbon atoms, and R 2 and R 4 each have 1 to 18 carbon atoms.
Represents an alkyl group or an alkoxy group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19588186A JPH0625868B2 (en) | 1986-08-20 | 1986-08-20 | Electrophotographic photoreceptor for positive charging |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19588186A JPH0625868B2 (en) | 1986-08-20 | 1986-08-20 | Electrophotographic photoreceptor for positive charging |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6350851A JPS6350851A (en) | 1988-03-03 |
| JPH0625868B2 true JPH0625868B2 (en) | 1994-04-06 |
Family
ID=16348539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19588186A Expired - Fee Related JPH0625868B2 (en) | 1986-08-20 | 1986-08-20 | Electrophotographic photoreceptor for positive charging |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625868B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018096916A (en) * | 2016-12-15 | 2018-06-21 | シスメックス株式会社 | Pre-treatment device and method for pre-treatment |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01269974A (en) * | 1988-04-21 | 1989-10-27 | Ricoh Co Ltd | Method for recovering fatigue of electrophotographic sensitive body |
| JP2810377B2 (en) * | 1988-05-16 | 1998-10-15 | 株式会社リコー | Electrophotographic photoreceptor fatigue recovery method |
| ES2147777T3 (en) | 1993-09-16 | 2000-10-01 | Ciba Sc Holding Ag | VINILETER COMPOUNDS WITH ADDITIONAL FUNCTIONAL GROUPS, OTHER THAN VINILETER, AND THEIR USE IN THE FORMULATION OF RETICULABLE COMPOUNDS. |
| TW382078B (en) * | 1994-06-10 | 2000-02-11 | Canon Kk | Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit |
| US6228546B1 (en) * | 1997-11-19 | 2001-05-08 | Canon Kabushiki Kaisha | Polymer, electrophotographic photosensitive member containing the polymer, process cartridge and electrophotographic apparatus having the electrophotographic photosensitive member |
-
1986
- 1986-08-20 JP JP19588186A patent/JPH0625868B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018096916A (en) * | 2016-12-15 | 2018-06-21 | シスメックス株式会社 | Pre-treatment device and method for pre-treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6350851A (en) | 1988-03-03 |
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