JPS6255662A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body having high sensitivity and superior durability and giving a clear image by forming an electrically conductive intermediate layer of NiP-Co on an electrically conductive substrate of Al or the like by electroless composite plating and by forming a photoconductive layer on the intermediate layer. CONSTITUTION:A thin NiP-Co film 4 and a photoconductive layer 3 are successively formed on an electrically conductive substrate 1 of Al or the like. The NiP-Co film is formed by adding Co particles to a warm bath contg. equimolar amounts of Ni and P compounds and a suitable complexing agent, immersing the substrate in the bath with stirring, and depositing Co in NiP by chemical reduction and compounding action. The NiP-Co film has superior uniformity, high adhesion and few pinholes. Though the thickness of the film is freely regulated, when the film is used as an element of an electrophotographic sensitive body, the thickness is required to be regulated to about 0.1-30mum.

Description

【発明の詳細な説明】 、産業上の利用分野 本発明は、電子写真法において用いられる感光体に関し
、詳しくはレーザプリンタ等の光プリンタの感光体に関
する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photoreceptor used in electrophotography, and more particularly to a photoreceptor for an optical printer such as a laser printer.

従来の技術 従来より画像形成法の１つとして電子写真法が広く知ら
れている。「電子写真法とは、一般に光導電性の感光体
をまず暗所で、例えばコロナ放電によって帯電せしめ、
次いで像露光し、露光部のみの電荷を選択的に逸散せし
めて静電潜像を得、この潜像部を染料、顔料などの着色
剤と高分子物質などの結合剤とから構成される検電微粒
子（トナー）で現像し、可視化して画像を形成する方法
である。2. Description of the Related Art Electrophotography has been widely known as one of the image forming methods. ``Electrophotography generally involves first charging a photoconductive photoreceptor in the dark, for example by means of corona discharge.
Next, image exposure is performed to selectively dissipate the charge only in the exposed areas to obtain an electrostatic latent image, and this latent image area is made up of a coloring agent such as a dye or pigment and a binder such as a polymeric substance. This is a method of developing with electrostatic fine particles (toner) and visualizing it to form an image.

このような電子写真法において用いられる感光体に要求
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
おいて電荷の逸散が少ないこと（３）光照射によってす
みやかに電荷を逸散せしめうろこと などがあげられる。The basic characteristics required of the photoreceptor used in such electrophotography are (1) ability to be charged to an appropriate potential in the dark, (2) low dissipation of charge in the dark, and (3) ability to resist light. Examples include scales that quickly dissipate charge when irradiated.

上記した特性を発揮させるためには、光導電材料の選択
、膜厚等が重要視されるが、導電性基体と光導電層との
間に介在する層（以下中間導電層と呼ぶ）の材料、膜厚
も重要である。即ち、同一光導電材料を導電性基体に、
同一膜厚に付着させた場合、中間導電層の材料が異なる
と、その電子写真特性、寿命が太き（変動する。In order to exhibit the above characteristics, importance is placed on the selection of photoconductive material, film thickness, etc., and the material of the layer interposed between the conductive substrate and the photoconductive layer (hereinafter referred to as the intermediate conductive layer) , film thickness is also important. That is, using the same photoconductive material as a conductive substrate,
When deposited to the same thickness, if the intermediate conductive layer is made of different materials, its electrophotographic characteristics and lifespan will vary.

ここで、中間導電層とは感光体上に帯電を与えた場合、
基体側からキャリアの移動を容易に行わしめるための層
である。Here, the intermediate conductive layer means that when a charge is applied to the photoreceptor,
This layer allows the carrier to easily move from the base side.

即ち電子写真手段においては、感光体上に帯電させ、こ
の帯電された電荷に基づき静電像が形成されるものであ
るが、帯電々荷を決定する一因は基体側からのキャリア
の注入によって定まるものである。従って、キャリアの
注入を良好にすることは極めて重要なことである。In other words, in electrophotography, a photoreceptor is charged and an electrostatic image is formed based on the charged charges, but one factor that determines the charge is the injection of carriers from the substrate side. It is determined. Therefore, it is extremely important to improve carrier injection.

また、この注入の程度は中間導電層の材料自体によるこ
とは勿論であるが、この他には基体及び光導電層との均
一な密着性によって定まるものである。The degree of this injection depends not only on the material of the intermediate conductive layer itself, but also on the uniform adhesion between the substrate and the photoconductive layer.

発明が解決しようとする問題点 ところで、従来この種の電子写真感光体の中間導電層は
、通常アルミニウム（以下ＡＩと略す）等の金属基体に
電気メツキ法やアルマイト法により薄膜を被覆して使用
されてきたが、厚さの不均一性、密着性の不良、また薄
膜にピンホールが発生する等の点で光導電層に安定した
特性が得られ難かった。Problems to be Solved by the Invention Incidentally, conventionally, the intermediate conductive layer of this type of electrophotographic photoreceptor has been used by coating a metal substrate such as aluminum (hereinafter abbreviated as AI) with a thin film by electroplating or anodizing. However, it has been difficult to obtain stable properties in the photoconductive layer due to nonuniform thickness, poor adhesion, and the occurrence of pinholes in the thin film.

そこで、本発明は先に述べた従来の感光体の中間導電層
のもつ種々の欠点を解消し、高感度、耐久性に優れ、か
つ画像鮮明な電子写真用感光体を提供することを目的と
する。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to eliminate the various drawbacks of the intermediate conductive layer of the conventional photoreceptor mentioned above, and to provide an electrophotographic photoreceptor with high sensitivity, excellent durability, and clear images. do.

問題点を解決するための手段 上記従来の問題を解決するため、本発明の電子写真感光
体は、ＡＩ等の導電性基体上に無電解複合メッキ法によ
りＮｉＰ−Ｃｏの中間導電層を形成し、更にその上に光
導電層を形成してなるものである。Means for Solving the Problems In order to solve the above conventional problems, the electrophotographic photoreceptor of the present invention has an intermediate conductive layer of NiP-Co formed on a conductive substrate such as AI by an electroless composite plating method. , and further a photoconductive layer is formed thereon.

作　　用 本構成により、高感度、長寿命２画像鮮明な電子写真感
光体を得ることができる。Function: With this configuration, an electrophotographic photoreceptor with high sensitivity, long life, and two clear images can be obtained.

実施例 第４図は、本発明の実施例における電子写真感光体の断
面図を示したものであり、図において１はＡＩ等の導電
性基体、４はＮｉＰ−Ｃｏ薄膜層、３は光導電層である
。また第３図は比較例を示す電子写真感光体であり、第
４図と異なる部分は第４図のＮｉＰ−Ｃｏ薄膜層４をＮ
ｉ薄膜層としたところである。Embodiment FIG. 4 shows a cross-sectional view of an electrophotographic photoreceptor in an embodiment of the present invention. In the figure, 1 is a conductive substrate such as AI, 4 is a NiP-Co thin film layer, and 3 is a photoconductive substrate. It is a layer. Further, FIG. 3 shows an electrophotographic photoreceptor showing a comparative example, and the difference from FIG. 4 is that the NiP-Co thin film layer 4 in FIG.
This is a thin film layer.

ところで、本発明に係るＮｉＰ−Ｃｏ薄膜の製法を簡単
に説明すると、Ｎｉ化合物とＰ化合物とを適当な錯化剤
と共に等モル数になるように配合した温浴中にＣｏ粒子
を添加し、撹拌しなからＡ１等の導電性基体を浸し、１
ヒ学的還元作用及び複合作用によりＮｉＰ中にＣｏを共
析させるものである。本性により得られるＮｉＰ−Ｃａ
′Ｐｔ膜は、均一１１１こ優れ、密着性大で、かつピン
ホールも極めて少ないという特徴を有する。By the way, to briefly explain the manufacturing method of the NiP-Co thin film according to the present invention, Co particles are added to a hot bath containing a Ni compound and a P compound mixed together with an appropriate complexing agent so that the number of moles is equal, and the mixture is stirred. Soak a conductive substrate such as A1 in the 1
Co is co-deposited into NiP by chemical reduction and combined action. NiP-Ca obtained by nature
'The Pt film is characterized by excellent uniformity, high adhesion, and extremely few pinholes.

尚、薄膜の厚さは自由におこなえるが、電子写真用の感
光体として用いる場合は、約０．１〜３０μｍの厚さの
範囲で形成すべきである。なぜなら、約０．１μｍ以下
より薄い場合は、中間導電層の作用は期待できず、また
３０μｍ以上の場合は電気的抵抗が大となって中間導電
層としての効果が発揮され難い。次に実験データを用い
て更に詳述する。The thickness of the thin film can be determined freely, but when used as a photoreceptor for electrophotography, it should be formed to a thickness of about 0.1 to 30 μm. This is because if the thickness is less than about 0.1 μm, no effect can be expected as an intermediate conductive layer, and if it is more than 30 μm, the electrical resistance becomes large and it is difficult to exhibit the effect as an intermediate conductive layer. Next, it will be explained in more detail using experimental data.

Ａ１金属板を次ベージの第１表に示す組成の無電解複合
メッキ液を用いて９０℃の温浴中に２０分間撹拌しなが
ら浸漬し、化学還元作用により約２μｍの厚さのＮｉＰ
−Ｃｏ薄膜をＡＩ金属板上に得た。この薄膜が形成され
たＡＩ金属板を試料第１表：無電解複合ＮｉＰ−Ｃｏメ
ッキ液八とする。An A1 metal plate was immersed in an electroless composite plating solution having the composition shown in Table 1 on the next page in a hot bath at 90°C for 20 minutes with stirring, and a NiP plate with a thickness of approximately 2 μm was formed by chemical reduction.
A -Co thin film was obtained on an AI metal plate. The AI metal plate on which this thin film was formed was designated as sample Table 1: Electroless composite NiP-Co plating solution 8.

次いでＡＩ金属板のみを試料Ｂとし、ＡＩ金属板上に電
気メツキ法によりＮｉ膜を約２μｍ設けたものを試料Ｃ
とした。Next, only the AI metal plate was designated as sample B, and the one on which a Ni film of approximately 2 μm was provided by electroplating on the AI metal plate was designated as sample C.
And so.

一方、光導電体としてフタロシアニン混合物（β型鋼フ
タロシアニンとＰＶＫ　（ポリビニルカルバゾール）、
その他）を上記試料Ａ、Ｂ、Ｃ上にワイヤーバーを用い
て塗布し、乾燥後の膜厚が約ｌＯμｍになるようにした
。On the other hand, a phthalocyanine mixture (β-type steel phthalocyanine and PVK (polyvinylcarbazole)) was used as a photoconductor.
Others) were applied onto the above samples A, B, and C using a wire bar so that the film thickness after drying was about 10 μm.

その後、８０℃で３時間乾燥し、２４時間以上暗中した
ものを試料とした。評価は、この３者の感光体に＋ＤＣ
６，５ＫＶコロナ帯電をさせ、次いで５Ｌｕｘ−ｓｅｃ
　（白色灯）の露光で電子写真特性（表面電位一時間）
を得た。（第１図）更に、これらの感光体に対し、ウレ
タンゴムブレードで１５０　ｇ　／　ｃｎ？の圧力を加
え摩擦させた場合の光導電膜の剥離特性を得た。（第２
図）尚、第１図及び第２図に於いてＩは本発明一実施例
に係る感光体く試料Ａ）の特性曲線図、■は中間導電層
としてＮｉメッキを施した感光体（試料Ｂ）の特１１曲
線図、■は中間導電層を有しない感光体（試料Ｃ）の特
性曲線図である。Thereafter, the sample was dried at 80° C. for 3 hours and left in the dark for 24 hours or more. The evaluation is +DC for these three photoconductors.
6.5KV corona charging, then 5Lux-sec
Electrophotographic characteristics (surface potential for one hour) with exposure to (white light)
I got it. (Figure 1) Furthermore, for these photoreceptors, 150 g/cn? The peeling characteristics of the photoconductive film were obtained when friction was applied to the photoconductive film. (Second
1 and 2, I is a characteristic curve diagram of a photoreceptor sample A) according to an embodiment of the present invention, and ■ is a characteristic curve diagram of a photoreceptor plated with Ni as an intermediate conductive layer (sample B). ) is a characteristic curve diagram of a photoreceptor (sample C) having no intermediate conductive layer.

実験の結果、試料Ａが試料Ｂ、試料Ｃに比較し、かなり
良い特性を得ることができた。これらの特性が得られた
理由をあげると、まず電子写真特性（表面電位一時間）
において試料への感光体は基板からのキャリアの注入が
良好なため、表面電位の向上が達成されたものと考えら
れる。As a result of the experiment, Sample A was able to obtain considerably better characteristics than Sample B and Sample C. The reasons why these properties were obtained are firstly the electrophotographic properties (surface potential for one hour).
It is thought that the improvement in surface potential was achieved because carrier injection from the substrate into the photoreceptor to the sample was good.

次に先導Ｔ、膜の剥離特性において、試料Ａの感光体は
ＡＩ金属板と中間導電層（ＮｉＰ−Ｃｏ薄膜）の密着性
が良好で、がっＮｉＰ−Ｃｏ薄膜の硬度が大（Ｈｖ５０
０）でビンポールが極めて少ない等の理由により、寿命
の向上が達成されたものと考えられる。Next, regarding the leading T and film peeling characteristics, the photoreceptor of Sample A has good adhesion between the AI metal plate and the intermediate conductive layer (NiP-Co thin film), and the hardness of the NiP-Co thin film is high (Hv50
0), it is thought that the improvement in life was achieved due to the extremely small number of bin poles.

発明の効果 以上の説明にて明らがとなったように、本発明の電子写
真感光体は、導電性金属基体表面にＮｉＰ−Ｃｏ薄膜を
被覆形成し、更にこのＮｉＰ−ＣＯ薄膜上に光導電層を
形成したものであり、中間導電体にＮｉＰ−Ｃｏを用い
たこ七により、導電性金属基体上光導電体との密着性、
均一膜性において優れ、またピンホールの発生も低減さ
れ、高感度、長寿命の電子写真感光体が提供でき、その
効果は非常に大きいものがある。Effects of the Invention As has become clear from the above explanation, the electrophotographic photoreceptor of the present invention has a NiP-Co thin film coated on the surface of a conductive metal substrate, and furthermore, a photoreceptor is formed on the NiP-Co thin film. A conductive layer is formed on the conductive metal substrate by using NiP-Co as the intermediate conductor, which improves the adhesion of the photoconductor on the conductive metal substrate.
It is possible to provide an electrophotographic photoreceptor that has excellent uniform film properties, reduces the occurrence of pinholes, has high sensitivity, and has a long life, and has very large effects.

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

第１図は電子写真感光体における露光時間−表面電位の
関係を示す特性曲線図（図中　Ｉは本発明一実施例に係
る感光体く試料Ａ）の特性曲線図、■は中間導電層とし
てＮｉメッキを施した感光体（試料Ｂ）の特性曲線図、
■は中間導電層を有しない感光体（試料Ｃ）の特性曲線
図を示す）第２図はウレタンゴムブレードによる摩擦回
数と光導電層の剥離状態との関係を示す特性図（但し、
図において１．ｎ、Ｉ［Ｉは第１図におけるＩ。 ■、■に同じ） 第３図は従来の電子写真感光体の断面図、第４図は本発
明一実施例に係る電子写真感光体の断面図である。 １・・・・Ａ１等の導電性金属基体 ２・・・・Ｎｉメッキ層　　　　　　３・・・・光導電
層４・・・・ＮｉＰ−Ｃｏ層FIG. 1 is a characteristic curve diagram showing the relationship between exposure time and surface potential in an electrophotographic photoreceptor (in the figure, I is a characteristic curve diagram of photoreceptor sample A according to one embodiment of the present invention), and ■ is a characteristic curve diagram showing the relationship between exposure time and surface potential in an electrophotographic photoreceptor. Characteristic curve diagram of the photoreceptor (sample B) plated with Ni,
(2) shows a characteristic curve diagram of a photoreceptor without an intermediate conductive layer (Sample C)) Figure 2 is a characteristic diagram showing the relationship between the number of times of friction with a urethane rubber blade and the peeling state of the photoconductive layer (However,
In the figure 1. n, I [I is I in FIG. 3 is a sectional view of a conventional electrophotographic photoreceptor, and FIG. 4 is a sectional view of an electrophotographic photoreceptor according to an embodiment of the present invention. 1... Conductive metal substrate such as A1 2... Ni plating layer 3... Photoconductive layer 4... NiP-Co layer

Claims (1)

【特許請求の範囲】[Claims] 導電性金属基板表面にＮｉＰ−Ｃｏ薄膜を被覆形成し、
更にこのＮｉＰ−Ｃｏ薄膜上に光導電層を形成したこと
を特徴とする電子写真感光体。Forming a NiP-Co thin film on the surface of a conductive metal substrate,
An electrophotographic photoreceptor further comprising a photoconductive layer formed on the NiP-Co thin film.