JPH01114855A - Electrophotographic sensitive body - Google Patents

Electrophotographic sensitive body

Info

Publication number
JPH01114855A
JPH01114855A JP27232187A JP27232187A JPH01114855A JP H01114855 A JPH01114855 A JP H01114855A JP 27232187 A JP27232187 A JP 27232187A JP 27232187 A JP27232187 A JP 27232187A JP H01114855 A JPH01114855 A JP H01114855A
Authority
JP
Japan
Prior art keywords
film
photoconductive layer
compd
oxide film
compound
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.)
Pending
Application number
JP27232187A
Other languages
Japanese (ja)
Inventor
Hiroichi Takenaka
博一 竹中
Takashi Atsumi
渥美 孝
Akira Hashimoto
明 橋本
Eizo Isoyama
礒山 永三
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Altemira Co Ltd
Original Assignee
Showa Aluminum Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Aluminum Corp filed Critical Showa Aluminum Corp
Priority to JP27232187A priority Critical patent/JPH01114855A/en
Publication of JPH01114855A publication Critical patent/JPH01114855A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • G03G5/142Inert intermediate layers

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

PURPOSE:To improve the bonding strength of a photosensitive layer to be formed on an anodized film on an Al base body to the anodized film by forming a specified film on said anodized film. CONSTITUTION:An anodized film 2, a film 3 comprising a specified mixture, and an undercoat layer 4 to be formed if necessary, and a photoconductive layer 5, are laminated in the order on a base body consisting of Al. The film 3 is constituted of a mixture of >=one kind of metal compd. (A), and a polymer (B) having OH groups, carboxyl groups, and acrylamide groups, and the amt. of the compd. (A) to be deposited is regulated to >=0.1mg/m<2>. It is preferred to use a Zr compd. (e.g. ammonium zirconium carbonate) or a Zr compd. in addn. to a Cr compd. for the compd. (A). Polyacrylamide, etc., is used for the polymer (B).

Description

【発明の詳細な説明】 産業上の利用分野 この発明は、静電式複写機あるいは電算機のプリンタ等
に使用される電子写真用感光体に関する。
DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to an electrophotographic photoreceptor used in electrostatic copying machines, computer printers, and the like.

なおこの明細書において、アルミニウムの語はその合金
を含む意味で用いる。
In this specification, the term aluminum is used to include its alloys.

従来の技術 上記のような用途に用いられる電子写真用感光体は、一
般に、アルミニウムからなる導電性支持体に、光導電性
絶縁材からなる光導電層を被覆したものに構成される。
2. Description of the Related Art Electrophotographic photoreceptors used for the above-mentioned purposes are generally constructed by covering a conductive support made of aluminum with a photoconductive layer made of a photoconductive insulating material.

而して従来、導電性支持体と光導電層との接着性を向上
するために、導電性支持体に下地処理として陽極酸化処
理を施し、支持体の表面に界面層としての未封孔陽極酸
化皮膜を形成し、該皮膜を介して光導電層を被覆形成し
たものが知られている(例えば特開昭61−19824
3号)。
Conventionally, in order to improve the adhesion between the conductive support and the photoconductive layer, the conductive support is anodized as a base treatment, and an unsealed anode is deposited on the surface of the support as an interface layer. It is known that an oxide film is formed and a photoconductive layer is coated through the film (for example, Japanese Patent Laid-Open No. 61-19824).
No. 3).

発明が解決しようとする問題点 ところが未封孔陽極酸化皮膜は、表面が吸着性に富み、
特に皮膜形成後直ちに光導電層を被覆形成する場合は確
かに光導電層との良好な接着性を実現しつるが、反面そ
の吸着性に富む性質の故に、皮膜形成後光導電層の被覆
形成までの期間が長いと良好な接着性が却って得られな
いという欠点があった。即ち実際の生産に際しては、導
電性支持体がその陽極酸化処理後、光導電層未形成のま
ま数日ないしは1か月程度あるいはそれ以上在庫され、
その後光導電層が成膜される場合がある。このような場
合、陽極酸化皮膜の優れた吸着性のため、在庫環境や在
庫期間によっては汚れや大気中の水分との反応による自
然封孔等を生じて、酸化皮膜の経時劣化を引起す結果、
所期のような良好な接着性が得られず、密着不良を起こ
すという問題があった。
Problems to be Solved by the Invention However, the unsealed anodic oxide film has a highly adsorbent surface.
In particular, if the photoconductive layer is formed immediately after the film is formed, good adhesion with the photoconductive layer can be achieved. If the period of time is long, there is a drawback that good adhesion cannot be obtained. That is, in actual production, after the conductive support is anodized, it is kept in stock for several days to a month or more without forming a photoconductive layer.
A photoconductive layer may then be deposited. In such cases, due to the excellent adsorption properties of the anodic oxide film, depending on the storage environment and storage period, natural sealing may occur due to reaction with dirt or moisture in the atmosphere, resulting in deterioration of the oxide film over time. ,
There was a problem in that the desired good adhesiveness could not be obtained and poor adhesion occurred.

しかもまた、導電性支持体と光導電層との間に陽極酸化
皮膜を介することによって、感光体の常温環境下での電
気的特性にも優れたものとなすことができるが、陽極酸
化皮膜の種類(特に硫酸皮膜)によっては高温、高湿環
境下で使用した場合、電気的特性が劣化し良好な画像特
性が得られないという問題もあった。
Moreover, by interposing an anodic oxide film between the conductive support and the photoconductive layer, the photoreceptor can have excellent electrical properties at room temperature. Depending on the type (particularly sulfuric acid film), when used in a high temperature and high humidity environment, there is a problem in that the electrical characteristics deteriorate and good image characteristics cannot be obtained.

一方また、導電性支持体と光導電層との接着性の更なる
向上及び電気的特性の向上を目的として、光導電層と陽
極酸化皮膜との間にアンダーコート層を設けることも行
われているが、この場合にも、陽極酸化処理後アンダー
コート層を設けるまでの期間が長いとやはりアンダーコ
ート層と陽極酸化皮膜との接着性が劣化し、また高温、
高湿環境下での使用の際に生じる電気的特性の劣化を防
ぐまでには至らないものであった。
On the other hand, an undercoat layer is also provided between the photoconductive layer and the anodic oxide film for the purpose of further improving the adhesion between the conductive support and the photoconductive layer and improving the electrical properties. However, even in this case, if the period between forming the undercoat layer after the anodizing treatment is long, the adhesion between the undercoat layer and the anodized film will deteriorate, and the high temperature,
It was not possible to prevent the deterioration of electrical characteristics that occurs when used in a high humidity environment.

この発明はかかる技術的背景に鑑みてなされたものであ
って、光導電層あるいはアンダーコート層との接着性に
優れるとともに、光導電層等を長期間経過後に被覆形成
した場合においても良好な接着性を維持でき、しかも高
温高湿環境下においても電気的性能の劣化を生じること
のない電子写真用感光体の提供を目的とするものである
This invention has been made in view of this technical background, and has excellent adhesion with the photoconductive layer or undercoat layer, and also has good adhesion even when the photoconductive layer etc. is coated after a long period of time. The object of the present invention is to provide an electrophotographic photoreceptor that maintains its properties and does not cause deterioration in electrical performance even under high temperature and high humidity environments.

問題点を解決するための手段 上記目的において、発明者は種々実験と研究を重ねた結
果、導電性支持体に形成された陽極酸化皮膜の表面に、
さらに接着性、はり水性に優れた、金属化合物と水酸基
若しくはカルボキシル基又はアクリルアミド基を有する
重合体との混合皮膜を、金属化合物の付着量を所定の範
囲に規定された状態に被覆形成することで、光導電層あ
るいはアンダーコート層の接着性の低下や、使用環境条
件の変化に伴う電気特性の劣化を防止しうることを知見
し、この発明を完成しえたものである。
Means for Solving the Problems For the above purpose, the inventor has conducted various experiments and research, and has found that the surface of the anodic oxide film formed on the conductive support,
Furthermore, by forming a mixed film of a metal compound and a polymer having a hydroxyl group, a carboxyl group, or an acrylamide group, which has excellent adhesiveness and water repellency, the amount of the metal compound adhered to is within a predetermined range. The present invention was completed based on the finding that it is possible to prevent a decrease in the adhesion of a photoconductive layer or an undercoat layer and a deterioration of electrical characteristics due to changes in usage environmental conditions.

即ち、この発明は第1図に示すように、アルミニウムか
らなる導電性支持体(1)に陽極酸化皮膜(2)が被覆
形成されるとともに、該陽極酸化皮膜の表面に、1種ま
たは2種以上の金属化合物と、水酸基若しくはカルボキ
シル基又はアクリルアミド基を有する重合体との混合皮
膜(3)が、前記金属化合物(金属化合物が2種以上含
まれる場合にはそのうちの少なくとも1種)の付着量を
0. 111tW/lri以上に規定された状態に被覆
形成され、該混合皮膜の上に光導電層(5)が形成され
てなることを特徴とする電子写真用感光体を要旨とする
ものである。
That is, as shown in FIG. 1, in this invention, a conductive support (1) made of aluminum is coated with an anodic oxide film (2), and one or two types of anodized film are coated on the surface of the anodic oxide film. The mixed film (3) of the above metal compound and a polymer having a hydroxyl group, a carboxyl group, or an acrylamide group has a coating amount of the metal compound (if two or more types of metal compounds are included, at least one of them). 0. The gist of the present invention is to provide an electrophotographic photoreceptor characterized in that it is coated with a concentration of 111 tW/lri or more, and a photoconductive layer (5) is formed on the mixed film.

導電性支持体(1)の構成材料として用いられるアルミ
ニウム材の種類は特に限定されるものではなく、加工性
、強度、硬さ等を考慮して市販の各種アルミニウム材の
中から適宜のものを選択使用すれば良い。−船釣には純
アルミニウム系、A3000番系等のアルミニウム展伸
材が好適に用いられる。また支持体の製造方法も問わな
い。
The type of aluminum material used as the constituent material of the conductive support (1) is not particularly limited, and an appropriate one may be selected from various commercially available aluminum materials in consideration of workability, strength, hardness, etc. You can use it selectively. - For boat fishing, aluminum wrought materials such as pure aluminum and A3000 series are preferably used. Furthermore, the method for manufacturing the support is not limited.

導電性支持体(1)の表面に被覆形成された陽極酸化皮
膜(2)の種類もまたこれを特定の皮膜に限定するもの
ではなく硫酸法、蓚酸法、クロム酸法等種々の陽極酸化
処理法の中から任意の処理法を用いて形成された皮膜で
良い。また陽極酸化処理条件も常法に従って設定すれば
良い。さらにはまた、陽極酸化皮膜(2)はこれを封孔
処理しても良く、あるいは未封孔のままでも良い。
The type of anodic oxidation film (2) formed on the surface of the conductive support (1) is not limited to a specific film, and various anodic oxidation treatments such as sulfuric acid method, oxalic acid method, chromic acid method, etc. A film formed using any treatment method among the above methods may be used. Further, the anodizing treatment conditions may be set according to a conventional method. Furthermore, the anodic oxide film (2) may be sealed or may be left unsealed.

陽極酸化皮膜(2)の表面に被覆形成された前記混合皮
膜(3)は、金属化合物と水酸基若しくはカルボキシル
基又はアクリルアミド基を有する重合体とが水溶液ある
いはエマルジョンの状態に混合された処理溶液の塗布、
乾燥工程を経て形成されるものである。ここで金属化合
物としては、好適なみのとしてジルコニウム化合物を挙
げつる。さらにジルコニウム化合物としては、例えばア
ンモニウムジルコニウムカーボネート、フルオロジルコ
ネートのアルカリ塩、アンモニウム塩、ジルコンふつ化
水素酸等を挙げうるが、特にジルコニウムのふつ化物を
用いた場合には、ふっ素の作用により、皮膜(3)自体
の導電性支持体(1)に対する接着性をより高いものと
なすことができる点で好ましい。
The mixed film (3) formed on the surface of the anodic oxide film (2) is formed by applying a treatment solution in which a metal compound and a polymer having a hydroxyl group, a carboxyl group, or an acrylamide group are mixed in an aqueous solution or emulsion state. ,
It is formed through a drying process. Here, as the metal compound, a zirconium compound is mentioned as a preferable example. Furthermore, examples of zirconium compounds include ammonium zirconium carbonate, alkali salts of fluorozirconate, ammonium salts, zirconium hydrofluoric acid, etc. However, when a zirconium fluoride is used in particular, the film is formed due to the action of fluorine. (3) It is preferable in that the adhesiveness of itself to the conductive support (1) can be made higher.

他の金属化合物としてはCr化合物を挙げうる。Other metal compounds include Cr compounds.

Cr化合物の具体例としては、3価あるいは6価のCr
を含む各種の塩や酸化物(例えばCr203)等を挙げ
うる。皮膜中に含有される金属化合物は1種のみでなく
2種以上であっても良い。2種以上の金属化合物の組み
合せの好適例として、ジルコニウム化合物とクロム化合
物の組み合せを挙げうる。
Specific examples of Cr compounds include trivalent or hexavalent Cr
Examples include various salts and oxides containing Cr203 (for example, Cr203). The number of metal compounds contained in the film may be not only one, but two or more. A preferred example of a combination of two or more metal compounds is a combination of a zirconium compound and a chromium compound.

一方、水酸基若しくはカルボキシル基を有する重合体と
しては、例えばポリアクリル酸、ポリビニルアルコール
、セルロースのヒドロキシエチルエーテル、エチレン無
水マレイン酸、ポリビニルピロリジン、ポリビニルメチ
ルエーテル等があり、使用しうる分散粒子型の重合体と
してはアクリル共重合ラテックス等がある。なかでもポ
リアクリル酸が好ましい。またアクリルアミド基ををす
る重合体とはいわゆるポリアクリルアミドをいう。
On the other hand, examples of polymers having hydroxyl or carboxyl groups include polyacrylic acid, polyvinyl alcohol, cellulose hydroxyethyl ether, ethylene maleic anhydride, polyvinylpyrrolidine, and polyvinylmethyl ether. Examples of the combination include acrylic copolymer latex. Among these, polyacrylic acid is preferred. Further, the polymer having an acrylamide group refers to so-called polyacrylamide.

上記のような金属化合物と、水酸基若しくはカルボキシ
ル基またはアクリルアミド基を有する重合体との処理液
中の混合割合は、金属化合物が1種の場合、皮膜中にお
ける金属化合物と重合体との含有比率が金属化合物1に
対して重合体0.5〜20となるような混合割合とする
のが良く、望ましくは1〜10となるような割合とする
のが良い。また2種の金属化合物が含有される場合にも
、皮膜中の含有比率が金属化合物の合計量1に対して重
合体0.5〜20、好ましくは1〜10となるような割
合で混合するのが良い。また処理液の塗布方法としては
、スプレー法、浸漬法、ロールコート法、へヶ塗り法等
任意の方法を採用しうる。また塗布後の乾燥は15〜3
00℃程度の温度で行うのが望ましい。乾燥時間は乾燥
温度によっても異なるが、例えば100〜150℃では
30秒程度行うのが良い。
The mixing ratio of the metal compound as described above and the polymer having a hydroxyl group, a carboxyl group, or an acrylamide group in the treatment liquid is determined based on the content ratio of the metal compound and the polymer in the film when there is only one type of metal compound. The mixing ratio is preferably 0.5 to 20 parts of the polymer to 1 part of the metal compound, preferably 1 to 10 parts. In addition, even when two types of metal compounds are contained, they are mixed at a ratio such that the content ratio in the film is 0.5 to 20, preferably 1 to 10, of the polymer to 1 of the total amount of metal compounds. It's good. Further, as a method for applying the treatment liquid, any method such as a spray method, a dipping method, a roll coating method, a dipping method, etc. can be adopted. Also, the drying time after application is 15 to 3
It is desirable to carry out the process at a temperature of about 00°C. Although the drying time varies depending on the drying temperature, for example, at 100 to 150°C, it is preferable to dry for about 30 seconds.

ところでこの発明では、前記混合皮膜(3)は、金属化
合物(2種以上の金属化合物が含まれる場合にはそのう
ちの少なくとも1種)がその付着量を0.  IIIt
g/rd以上に規定された状態に形成されることを要件
とする。金属付着量をこのように設定するのは、次の理
由による。即ち、混合皮膜(3)を被覆することで、長
期間経過後光導電層やアンダーコート層を形成しても良
好な接着性を保持でき、また高温、高湿環境下での電気
的特性の劣化を生じないものとなしうる理由の1つとし
て、該混合皮膜がはり水性皮膜であることが考えられる
が、金属化合物の付着量が0.  IIIIy/rd未
満では、良好なはっ水性が得られず、ひいては光導電層
との接着不良等を生ずるからである。一方送に多くなっ
ても該効果の格別な増大がなく、むしろ材料の無駄によ
るコストアップの欠点を派生する。好ましい付着量の範
囲はいずれの金属化合物についても0.5〜500rr
rg#である。金属化合物の付着量の設定は、処理溶液
の製作段階において金属化合物と水酸基若しくはカルボ
キシル基またはアクリルアミド基を有する重合体との混
合比率の設定によって行っても良く、あるいは処理溶液
の導電性支持体への塗布量の調整によって行っても良い
。また最終的な皮膜量は、0゜5〜5000111g/
mとするのが接着性等の向上効果をより発揮しうる点で
好ましく、特に1〜1100OIrt/mとするのが良
い。
By the way, in the present invention, the mixed film (3) has a metal compound (if two or more types of metal compounds are included, at least one of them) with an adhesion amount of 0. IIIt
It is required to be formed in a state specified by g/rd or more. The reason for setting the metal adhesion amount in this way is as follows. That is, by coating the mixed film (3), it is possible to maintain good adhesion even after forming a photoconductive layer or an undercoat layer after a long period of time, and it is possible to maintain good electrical properties in high temperature and high humidity environments. One of the reasons why it does not cause deterioration is that the mixed film is a water-based film, but if the amount of metal compound deposited is 0. This is because, if it is less than IIIy/rd, good water repellency cannot be obtained, resulting in poor adhesion to the photoconductive layer. Even if the number of one-way feeds is increased, the effect will not be particularly increased, but rather the disadvantage of increased costs due to wasted material will result. The preferred range of coating amount is 0.5 to 500rr for any metal compound.
rg#. The amount of the metal compound deposited may be set by setting the mixing ratio of the metal compound and a polymer having a hydroxyl group, a carboxyl group, or an acrylamide group during the production stage of the treatment solution, or by setting the amount of the metal compound attached to the conductive support of the treatment solution. This may be done by adjusting the amount of coating. The final coating amount is 0°5~5000111g/
It is preferable to set it to 1-1100 OIrt/m in terms of being able to more effectively exhibit the effect of improving adhesiveness, etc., and it is particularly good to set it to m.

光導電層(5)は前記混合皮膜(3)の表面に直接的に
被覆形成されても良く、あるいは図面に示すように、ア
ンダーコート層(4)を介して被覆形成されても良い。
The photoconductive layer (5) may be directly coated on the surface of the mixed film (3), or may be coated via an undercoat layer (4) as shown in the drawings.

光導電層(5)の種類は特に限定されるものではなく、
セレン系材料、アモルファスシリコン系材料、有機物系
材料等いずれを用いても良い。またアンダーコート層は
一般的にはポリアミド系樹脂により構成される。
The type of photoconductive layer (5) is not particularly limited,
Any of selenium-based materials, amorphous silicon-based materials, organic materials, etc. may be used. Further, the undercoat layer is generally made of polyamide resin.

発明の効果 この発明は上述の次第で、アルミニウムからなる導電性
支持体に陽極酸化皮膜が被覆形成されるとともに、該陽
極酸化皮膜の表面に1種または2種以上の金属化合物と
、水酸基若しくはカルボキシル基またはアクリルアミド
基を有する重合体との混合皮膜が、前記金属化合物(金
属化合物が2種以上含まれる場合にはそのうちの少なく
とも1種)の付着量を0. 1111/rd以上に規定
された状態に被覆形成され、該混合皮膜の上に光導電層
が形成されてなることを特徴とするものである。従って
後述の実施例の参酌によっても明らかなように、混合皮
膜形成後直ちに光導電層やアンダーコート層を形成した
場合はもとより、長期間経過後形成した場合であっても
導電性支持体と光導電層との充分な接着性を保持しえ、
光導電層の別離、ふくれ、亀裂等の現象を生じることの
ない安定した感光体となしうる。さらにまた、陽極酸化
皮膜表面に混合皮膜を形成することで、特に陽極酸化皮
膜が硫酸皮膜である場合に従来認められたような高温、
高湿環境下での電気的性能の劣化を引き起こすことがな
く、使用環境条件の如何を問わず優れた電気的性能を発
揮し、ひいては優れた画像特性を有する感光体となしつ
る。
Effects of the Invention As described above, the present invention includes forming an anodic oxide film on a conductive support made of aluminum, and coating the surface of the anodic oxide film with one or more metal compounds and a hydroxyl group or a carboxyl group. The mixed film with a polymer having a group or an acrylamide group reduces the adhesion amount of the metal compound (at least one of the metal compounds when two or more types are included) to 0. It is characterized in that it is coated in a state defined by 1111/rd or more, and a photoconductive layer is formed on the mixed film. Therefore, as is clear from consideration of the Examples described later, not only when the photoconductive layer and undercoat layer are formed immediately after forming the mixed film, but also when the photoconductive layer and undercoat layer are formed after a long period of time, the conductive support and the Maintains sufficient adhesion with the conductive layer,
A stable photoreceptor can be obtained without causing phenomena such as separation, blistering, and cracking of the photoconductive layer. Furthermore, by forming a mixed film on the surface of the anodic oxide film, high temperatures and
The photoreceptor does not cause deterioration of electrical performance in a high humidity environment, exhibits excellent electrical performance regardless of the environmental conditions in which it is used, and has excellent image characteristics.

実施例 次にこの発明の実施例を比較例との対比において示、す
EXAMPLES Next, examples of the present invention will be shown in comparison with comparative examples.

A3003アルミニウム合金を、常法により押出バイブ
に押出したのち引抜き加工を施し、さらにその後切削を
実施してその表面を表面粗さ0.ISに平滑仕上げした
ものを導電性支持体として用いた。
A3003 aluminum alloy was extruded into an extrusion vibrator using a conventional method, then subjected to drawing processing, and then cut to a surface roughness of 0. An IS with a smooth finish was used as a conductive support.

そして上記支持体を複数個用意し、それぞれに硫酸濃度
:15%、液温:20±1℃の硫酸電解液中で電流密度
; 1. 3A/dTIl、処理時間20分の条件で陽
極酸化処理を実施して硫酸陽極酸化皮膜を被覆形成した
A plurality of the above-mentioned supports were prepared, and each was subjected to a current density in a sulfuric acid electrolyte having a sulfuric acid concentration of 15% and a liquid temperature of 20±1°C; 1. Anodic oxidation treatment was carried out under conditions of 3 A/dTIl and a treatment time of 20 minutes to form a sulfuric acid anodic oxide film.

次いで、半数の導電性支持体については、圧力4Kgf
/cIIIの加圧蒸気処理による封孔処理を25分間実
施した。また他の半数については封孔処理を実施しなか
った。その後以下に示す処理をした。
Then, for half of the conductive supports, the pressure was 4 Kgf.
/cIII pressurized steam treatment was performed for 25 minutes. The other half of the holes were not sealed. After that, the following processing was performed.

(実施例1) まず、下記に示すような性状を有する炭酸アンモンジル
コニウムとポリアクリルアミドの含有溶液(A)を用意
した。
(Example 1) First, a solution (A) containing ammonium zirconium carbonate and polyacrylamide having the properties shown below was prepared.

溶液(A)の性状 PH:8.1 (25℃において) 粘度:23cP(27℃において) 炭酸アンモンジルコニウム量:(ジルコニウムで0.3
%) ポリアクリルアミド量:5% そして上記溶液(A)を1、水を2の割合で混合して処
理液とした。次いでこの処理液を導電性支持体の陽極酸
化皮膜表面にゴムロールにて塗布したのち、150℃×
20秒間の乾燥を行って、ジルコニウム化合物とポリア
クリルアミドとの混合皮膜を形成した。このときの皮膜
量は100111ff#であり、炭酸アンモンジルコニ
ウムの付着量は約5η/TItであった。
Properties of solution (A) PH: 8.1 (at 25°C) Viscosity: 23 cP (at 27°C) Amount of ammonium zirconium carbonate: (0.3 in zirconium)
%) Amount of polyacrylamide: 5% Then, one part of the solution (A) and two parts of water were mixed to prepare a treatment liquid. Next, this treatment solution was applied to the surface of the anodic oxide film of the conductive support using a rubber roll, and then heated at 150°C.
Drying was performed for 20 seconds to form a mixed film of zirconium compound and polyacrylamide. The amount of film at this time was 100111ff#, and the amount of ammonium zirconium carbonate deposited was about 5η/TIt.

モして封孔処理したもの及び未封孔のものそれぞれにつ
いて、混合皮膜形成後すぐにアンダーコート層を厚さ約
1μmに被覆形成したものと、混合皮膜形成後温度25
℃、湿度70%の環境下にて30日間放置したのち同じ
くアンダーコート層を被覆形成したものを製作した。ア
ンダーコート層の形成は、ポリアミド系樹脂の塗布、乾
燥により行った。
For the pore-sealed one and the unsealed one, one was coated with an undercoat layer to a thickness of about 1 μm immediately after forming the mixed film, and the other was coated with an undercoat layer to a thickness of about 1 μm after forming the mixed film.
After being left for 30 days in an environment of 70% humidity and 70% temperature, a similar undercoat layer was formed. The undercoat layer was formed by applying and drying a polyamide resin.

その後、光導電層としてポリビニール力ルバゾール/ト
リニトロフルオレノン(PVK/TNF)を被覆形成し
、本発明に係る感光体を得た(試料N o 1〜4 )
 oなおPVK/TNFの被覆形成はいずれも浸漬法に
よる塗布をもって行い、層厚はいずれも15μmとした
Thereafter, polyvinyl Rubazol/trinitrofluorenone (PVK/TNF) was coated as a photoconductive layer to obtain photoreceptors according to the present invention (Samples No. 1 to 4).
The PVK/TNF coating was formed by dipping, and the layer thickness was 15 μm in each case.

(実施例2) 下記に示すような性状を有するぶつ化ジルコニウム化合
物とポリアクリルアミドの含有溶液(B)、及びふり化
クロム化合物の含有溶液(C)を用意した。
(Example 2) A solution (B) containing a fluorinated zirconium compound and polyacrylamide and a solution (C) containing a fluorinated chromium compound having the properties shown below were prepared.

溶液(B)の性状 PH: 5.2 (25℃において) 粘度:16cP(27℃において) 比重: 1.025 (27℃において)分子量:5〜
lO万 ぶつ化ジルコニウムffi: (ジルコニウムで0.5
%) ポリアクリルアミド量:5% クロム量70.83% Fの濃度=0.9% そして、溶液(B)を5、溶液(C)を1、水を10の
割合で混合して処理液とし、該処理液を導電性支持体の
陽極酸化皮膜表面にゴムロールにて塗布したのち、15
0℃X20秒間の乾燥を行って、ジルコニウム化合物及
びクロム化合物とポリアクリルアミドとの混合皮膜を形
成した。このときの皮膜量は60rIrg/mであった
。またジルコニウム化合物の付着量は51ng/d1ク
ロム化合物の付着量は2η/ゴであった。
Properties of solution (B) PH: 5.2 (at 25°C) Viscosity: 16 cP (at 27°C) Specific gravity: 1.025 (at 27°C) Molecular weight: 5-
Zirconium oxide ffi: (Zirconium 0.5
%) Amount of polyacrylamide: 5% Amount of chromium: 70.83% Concentration of F = 0.9% Then, mix 5 parts of solution (B), 1 part of solution (C), and 10 parts of water to prepare a treatment liquid. , After applying the treatment liquid to the surface of the anodic oxide film of the conductive support using a rubber roll,
Drying was performed at 0° C. for 20 seconds to form a mixed film of a zirconium compound, a chromium compound, and polyacrylamide. The coating amount at this time was 60 rIrg/m. The amount of the zirconium compound attached was 51 ng/d1, and the amount of the chromium compound attached was 2η/g.

そして実施例1と同じく、封孔処理したもの及び未封孔
のものそれぞれについて、混合皮膜形成後すぐにアンダ
ーコート層を実施例1と同一条件で被覆形成したものと
、混合皮膜形成後温度25℃、湿度70%の環境下にて
30日間放置したのち同じくアンダーコート層を被覆形
成したものを製作した。
As in Example 1, the sealed and unsealed ones were coated with an undercoat layer immediately after forming the mixed film under the same conditions as in Example 1, and the mixed film was formed at a temperature of 25°C. After being left for 30 days in an environment of 70% humidity and 70% temperature, a similar undercoat layer was formed.

その後、光導電層としてPVK/TNFを前記と同一条
件で被覆形成して本発明に係る感光体を得た(試料No
5〜8)。
Thereafter, PVK/TNF was coated as a photoconductive layer under the same conditions as above to obtain a photoreceptor according to the present invention (Sample No.
5-8).

(実施例3) 陽極酸化皮膜の表面に、10%(V/V)希釈において
第1表のような組成を有する処理液を用いて、165グ
ラビアメツシユロールコートを施し、次いで150℃X
30秒乾燥してクロム化合物とカルボキシル基を有する
重合体との混合皮膜を被覆形成した。このときのクロム
化合物付着量は約2mg/rrrであった。
(Example 3) A 165 gravure mesh roll coat was applied to the surface of the anodic oxide film using a treatment solution having a composition as shown in Table 1 at 10% (V/V) dilution, and then 150°C
It was dried for 30 seconds to form a mixed film of a chromium compound and a polymer having a carboxyl group. The amount of chromium compound deposited at this time was about 2 mg/rrr.

第1表 そして実施例1と同じく、封孔処理したもの及び未封孔
のものそれぞれについて、混合皮膜形成後すぐにアンダ
ーコート層を実施例1と同一条件で被覆形成したものと
、混合皮膜形成後温度25℃、湿度70%の環境下にて
30日間放置したのち同じくアンダーコート層を被覆形
成したものを製作した。
As in Table 1 and Example 1, for the sealed and unsealed ones, the undercoat layer was immediately coated under the same conditions as Example 1 after forming the mixed film, and the mixed film was formed. After leaving it for 30 days in an environment with a temperature of 25° C. and a humidity of 70%, a similar undercoat layer was formed.

その後、光導電層としてPVK/TNFを前記と同一条
件で被覆形成して本発明に係る感光体を得た(試料No
9〜12)。
Thereafter, PVK/TNF was coated as a photoconductive layer under the same conditions as above to obtain a photoreceptor according to the present invention (Sample No.
9-12).

[比較例] 混合皮膜を形成することなく、封孔処理したもの及び未
封孔のものそれぞれについて、陽極酸化皮膜形成後すぐ
にアンダーコート層を実施例と同一条件で被覆形成した
ものと、陽極酸化皮膜形成後温度25℃、湿度70%の
環境下にて30日間放置したのちアンダーコート層を被
覆形成したものを製作した。
[Comparative Example] For each of the pore-sealing treated without forming a mixed film and the unsealed pore, one was coated with an undercoat layer under the same conditions as the example immediately after forming the anodic oxide film, and the other was anodized. After forming the oxide film, it was allowed to stand for 30 days in an environment with a temperature of 25° C. and a humidity of 70%, and then an undercoat layer was formed on it to produce a product.

その後、光導電層としてPVK/TNFを前記と同一条
件で被覆形成して比較界としての感光体を得た(試料N
o13〜1B)。
Thereafter, PVK/TNF was coated as a photoconductive layer under the same conditions as above to obtain a photoconductor for comparison (Sample N
o13-1B).

以上により得た各感光体につき、その製作途中においで
あるいは完成後において、下記の試験を実施した。
The following tests were conducted on each of the photoreceptors obtained as described above, either during the production or after completion.

[混合皮膜のはり水性調査コ 各混合皮膜につき、その表面に純水を2μΩ垂らし、1
分後の接触角を測定した。なお比較品については、陽極
酸化皮膜表面において調査した。
[Water-based investigation of mixed films] For each mixed film, drop 2 μΩ of pure water on the surface,
The contact angle was measured after 10 minutes. For comparison products, the surface of the anodic oxide film was investigated.

[接着性試験] アンダーコート層の被覆形成後テープ剥離試験を実施し
た。
[Adhesion Test] After forming the undercoat layer, a tape peeling test was conducted.

[画像性能コ 各感光体につき、0刷りにおける黒点発生状況を調査し
た。調査は温度及び湿度を変えた2種類の環境条件のも
とで行った。
[Image performance] For each photoreceptor, the occurrence of black spots during the zero printing was investigated. The study was conducted under two different environmental conditions, varying temperature and humidity.

以上の結果を下記第2表に示す。The above results are shown in Table 2 below.

[以下余白] 上記結果から明らかなように、本発明実施品では金属化
合物と、水酸基若しくはカルボキシル基又はアクリルア
ミド基を有する重合体との混合皮膜のはり水性が良く、
また混合皮膜形成後アンダーコート層の被覆形成までの
時間が長い場合であっても直ちに被覆形成した場合と同
じく、導電性支持体とアンダーコート層との接着性、従
って該支持体と光導電層との接着性に優れたものである
ことがわかる。しかも、感光体の使用環境条件が悪くて
も感光体の電気的性能の劣化ひいては画像特性の劣化を
生じないこともわかる。
[Blank below] As is clear from the above results, in the product of the present invention, the mixed film of a metal compound and a polymer having a hydroxyl group, a carboxyl group, or an acrylamide group has good water repellency;
In addition, even if it takes a long time to form the undercoat layer after forming the mixed film, the adhesion between the conductive support and the undercoat layer will be affected, as in the case where the coating is formed immediately. It can be seen that it has excellent adhesion with Furthermore, it can be seen that even if the environmental conditions in which the photoreceptor is used are bad, there is no deterioration in the electrical performance of the photoreceptor, and hence there is no deterioration in the image characteristics.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図はこの発明に係る感光体の一実施例を示す部分拡
大断面図である。 (1)・・・導電性支持体、(2)・・・陽極酸化皮膜
、(3)・・・混合皮膜、(4)・・・アンダーコート
層、(5)・・・光導電層。 以上
FIG. 1 is a partially enlarged sectional view showing an embodiment of a photoreceptor according to the present invention. (1) Conductive support, (2) Anodic oxide film, (3) Mixed film, (4) Undercoat layer, (5) Photoconductive layer. that's all

Claims (3)

【特許請求の範囲】[Claims] (1)アルミニウムからなる導電性支持体に陽極酸化皮
膜が被覆形成されるとともに、該陽極酸化皮膜の表面に
、1種または2種以上の金属化合物と、水酸基若しくは
カルボキシル基又はアクリルアミド基を有する重合体と
の混合皮膜が、前記金属化合物(金属化合物が2種以上
含まれる場合にはそのうちの少なくとも1種)の付着量
を0.1mg/m^2以上に規定された状態に被覆形成
され、該混合皮膜の上に光導電層が形成されてなること
を特徴とする電子写真用感光体。
(1) An anodic oxide film is coated on a conductive support made of aluminum, and the surface of the anodic oxide film is coated with one or more metal compounds and a heavy metal compound having a hydroxyl group, a carboxyl group, or an acrylamide group. A mixed film with coalescence is formed to coat the metal compound (if two or more metal compounds are included, at least one of them) in a state in which the amount of adhesion is regulated to be 0.1 mg/m^2 or more, A photoreceptor for electrophotography, characterized in that a photoconductive layer is formed on the mixed film.
(2)金属化合物がジルコニウム化合物である特許請求
の範囲第1項記載の電子写真用感光体。
(2) The electrophotographic photoreceptor according to claim 1, wherein the metal compound is a zirconium compound.
(3)金属化合物がジルコニウム化合物及びクロム化合
物である特許請求の範囲第1項記載の電子写真用感光体
(3) The electrophotographic photoreceptor according to claim 1, wherein the metal compound is a zirconium compound and a chromium compound.
JP27232187A 1987-10-28 1987-10-28 Electrophotographic sensitive body Pending JPH01114855A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27232187A JPH01114855A (en) 1987-10-28 1987-10-28 Electrophotographic sensitive body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27232187A JPH01114855A (en) 1987-10-28 1987-10-28 Electrophotographic sensitive body

Publications (1)

Publication Number Publication Date
JPH01114855A true JPH01114855A (en) 1989-05-08

Family

ID=17512252

Family Applications (1)

Application Number Title Priority Date Filing Date
JP27232187A Pending JPH01114855A (en) 1987-10-28 1987-10-28 Electrophotographic sensitive body

Country Status (1)

Country Link
JP (1) JPH01114855A (en)

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