JPS60119571A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve the current rectifying characteristic between a base body and a photoconductive layer by providing an intermediate layer consisting of a thin amorphous Ni-B film or thin Ni-B alloy film between a conductive base body and the photoconductive layer. CONSTITUTION:An intermediate layer 2 consisting of a thin amorphous Ni-B film or thin Ni-B alloy film is formed by an electroless plating method, vapor deposition method, sputtering method, etc. on a conductive base body consisting of aluminum or the like. A photoconductive laye 3 consisting of Se, SeTe, etc. is then formed on the layer 2 to manufacture an intended electrophotographic sensitive body. The efficiency of hole implantation from the base body 1 is considerably increased by the presence of the Ni-B intermediate layer 2 without spoiling the electrostatic characteristic of the layer 3 and therefore the characteristic required for a composite photosensitive body for two-color copying is substantially satisfied. The layer 2 is easily industrially formable if an electroless plating method is used.

Description

【発明の詳細な説明】 〔技術分野〕 本発明は２色電子写真感光体さらに詳しくは導電性基体
表面をＮｉ−Ｂ非品質または合金薄膜で被覆した電子写
真感光体に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a two-color electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a conductive substrate surface coated with a Ni-B non-quality or alloy thin film.

〔従来技術〕[Prior art]

従来、導電性基体と光導電層との間に中間層を設けて基
体側からキャリヤの移動を容易に行なわしめることが知
られている。この種の中間層のうち、特に光導電層との
仕事関数との関係に着目した中間層としてＩＪｉ−Ｐ合
金を用いてキャリヤの注入性を改善する方法が提案され
ている《特公昭５１−３５８６４号公報参照》。しかし
ながらＮｉ−Ｐ合金を中間層として）ｌ基質上に設けそ
の上にＡＳ２Ｓｅ３からなる光導電層を設けた感光体の
負帯電特性は一２００ｖ以下であってホ−ルの注入が充
分とはいえない。また、仕事関数が感光層物質以下でＮ
１以上の金属、Ｔｅ以上のカルコゲン物質、Ａ８以上の
粉末および結着樹脂からガる中間層を用いることが提案
されている（特公昭５４−３６８５９号公報参照）。し
かしながら、この方法では結着樹脂を使用するためＡｓ
２Ｓｅ３などの光導電層では形成条件が制約され満足す
べき電気特性が得られないという欠点がある。Conventionally, it has been known to provide an intermediate layer between a conductive substrate and a photoconductive layer to facilitate the movement of carriers from the substrate side. Among these types of intermediate layers, a method has been proposed to improve the carrier injection property by using an IJi-P alloy as an intermediate layer, paying particular attention to the relationship between the work function and the photoconductive layer. See Publication No. 35864》. However, the negative charging characteristic of a photoreceptor with a Ni-P alloy as an intermediate layer on a substrate and a photoconductive layer made of AS2Se3 on top of it is less than -200V, and hole injection is sufficient. do not have. Also, if the work function is less than the photosensitive layer material, N
It has been proposed to use an intermediate layer made of one or more metals, a chalcogen substance of Te or more, a powder of A8 or more, and a binder resin (see Japanese Patent Publication No. 54-36859). However, since this method uses a binder resin, As
A photoconductive layer made of 2Se3 or the like has a disadvantage in that the formation conditions are restricted and satisfactory electrical properties cannot be obtained.

〔目　的〕〔the purpose〕

本発明は上記現状に鑑みてなされたものであって、その
目的は電子写真感光体の基体および光導電層間の整流特
性を改善することである。The present invention has been made in view of the above-mentioned current situation, and its purpose is to improve the rectification characteristics between the substrate and the photoconductive layer of an electrophotographic photoreceptor.

〔構　成〕〔composition〕

上記目的を達成するために、本発明は電子写真感光体に
おける中間層としてＮ１−Ｂ非晶質薄膜またはＮ１−Ｂ
合金薄膜を用いることにある。In order to achieve the above object, the present invention provides an N1-B amorphous thin film or a N1-B amorphous thin film as an intermediate layer in an electrophotographic photoreceptor.
The purpose is to use an alloy thin film.

本発明の電子写真感光体はＮ１−Ｂ非晶質薄膜またはＮ
１−Ｂ合金薄膜を被覆した導電性基体表面に光導電層を
設けたものを基本とする。また、本発明の電子写真感光
体の別の態様として、光導電層を第１光導電層と第２光
導電層との２層構成にすることができる。第１光導電層
はＮ１−Ｂ非晶質薄膜またはＮ１−Ｂ合金薄膜を被覆し
た導電性基体表面の上に設けられそして第２光導電層は
該第１光導電層の上に設けられる。また、第２光導電層
は可視光領域の一部有彩色光に対し感度を有し且つ他の
有彩色光を透過するものであシ、一方第１光導電層は少
なくともその第２光導電層を透過する有彩色光に対し感
度を有するものである。The electrophotographic photoreceptor of the present invention is an N1-B amorphous thin film or an N
Basically, a photoconductive layer is provided on the surface of a conductive substrate coated with a 1-B alloy thin film. In another embodiment of the electrophotographic photoreceptor of the present invention, the photoconductive layer can have a two-layer structure of a first photoconductive layer and a second photoconductive layer. A first photoconductive layer is disposed on a conductive substrate surface coated with an N1-B amorphous film or a N1-B alloy thin film, and a second photoconductive layer is disposed on the first photoconductive layer. Further, the second photoconductive layer is sensitive to some chromatic light in the visible light range and transmits other chromatic light, while the first photoconductive layer is sensitive to at least the second photoconductive layer. It is sensitive to chromatic light that passes through the layer.

次に、図面を参照して本発明の電子写真感光圧について
具体的に説明する。Next, the electrophotographic photosensitive pressure of the present invention will be specifically explained with reference to the drawings.

第１図に示すように、本発明の電子写真感光体は導電性
基体１の上に中間層２を設けさらにその上に光導電層３
を設けたものが基本構成である。導電性基体としては例
えばＡｌ、ステンレススチールなどの金属板、５ｎ０２
、Ｉｎ２Ｏ５などの金属酸化物あるいはこれら金属また
は金属酸化物を被覆したプラスチックフィルム、紙また
は布などを用いることができる。中間層はＮｉ　−Ｂ非
晶質薄膜またはＮ１−Ｂ合金薄膜からなる。中間層は例
えば蒸着法、スパッタリング法など通常の方法によって
形成することができるが、工業的には無電解メッキ法が
最も有利である。中間層の膜厚は５ｏｏｏＡ〜１０μ好
ましくは１μ〜５μの範囲にある。例えばアルカリ性ニ
ッケルメッキ液を用いる場合、Ｎ１−Ｂの還元析出反応
は以下の反応式で表わすことができる。As shown in FIG. 1, the electrophotographic photoreceptor of the present invention has an intermediate layer 2 on a conductive substrate 1, and a photoconductive layer 3 on top of the intermediate layer 2.
The basic configuration is as follows. Examples of the conductive substrate include metal plates such as Al and stainless steel, and 5n02.
, In2O5, or other metal oxides, or plastic films, paper, or cloth coated with these metals or metal oxides can be used. The intermediate layer consists of a Ni-B amorphous thin film or an N1-B alloy thin film. The intermediate layer can be formed by conventional methods such as vapor deposition and sputtering, but electroless plating is industrially most advantageous. The thickness of the intermediate layer is in the range of 500A to 10μ, preferably 1μ to 5μ. For example, when using an alkaline nickel plating solution, the reduction and precipitation reaction of N1-B can be expressed by the following reaction formula.

４ＮｉＣｔ２　＋ＮａＢＯ２＋　８ＮａＯＨ−＋４Ｎｉ
　＋ＮａＢＯ２＋　８ＮａＣ４＋　６Ｈ２０４ＮｉＣ１
２＋２ＮａＢＨ４＋６ＮａＯＨ→２Ｎｉ２Ｂ＋Ｈ２，、
＋ｌ８ＮａＣｌ＋、６Ｈ２０得られたＮ１−Ｂ膜の構造
は非晶質であるが、非晶質でも整流性は大巾に改善され
て所望の電気特性を得ることができる。メッキ後、Ｎ１
−Ｂ膜に後処理を施すとＮｉ　−Ｂ合金となるが非晶質
膜と同等の整流性を維持し且つ導電性基体との密着性の
向上およびＮ１−Ｂ膜中の応力の解放などを図ることが
可能となる。また、光導電層としてはＳｅ系憑光層を用
いることができ、その代表的な例としてはＳｅ％５ｅＴ
ｅ、　Ａｓ２Ｓｅ３．５ｅ−Ｂｉ、５ｅ−８ｂなどをあ
げることができる。4NiCt2 +NaBO2+ 8NaOH-+4Ni
+NaBO2+ 8NaC4+ 6H204NiC1
2+2NaBH4+6NaOH→2Ni2B+H2,,
+l8NaCl+, 6H20 The structure of the obtained N1-B film is amorphous, but even if it is amorphous, the rectification properties are greatly improved and desired electrical characteristics can be obtained. After plating, N1
When the -B film is post-treated, it becomes a Ni-B alloy, which maintains the same rectification properties as an amorphous film, improves adhesion to the conductive substrate, and releases stress in the N1-B film. It becomes possible to achieve this goal. Furthermore, a Se-based photoconductive layer can be used as the photoconductive layer, and a typical example thereof is Se%5eT
Examples include As2Se3.5e-Bi, 5e-8b, etc.

第２図は本発明による電子写真感光体の別の態様を示す
ものであって、導電性基体１の上に中間層２を設けさら
にその上に第１光導電層４および第２光導電層５を設け
たものである。第１光導電層は上記光導電層と同様にＳ
ｅ系感光層であって、その膜厚は１０〜１５０μ好まし
くは５０〜１２０μの範囲にある。また、第２光導電層
としては正または負の帯電下あるいは両極性帯電下で可
視光領域の一部有彩色光によシ導体化するような光導電
性部材が用いられる。特に両極性帯電下で光導電性を示
す材料としてはフタロシアニン顔料、アゾ顔料のような
有機顔料、ピリリウム系染料およびこれら染料と樹脂と
の共晶錯体、電荷移動錯体などをあげることができる。FIG. 2 shows another embodiment of the electrophotographic photoreceptor according to the present invention, in which an intermediate layer 2 is provided on a conductive substrate 1, and a first photoconductive layer 4 and a second photoconductive layer are further provided thereon. 5. The first photoconductive layer is S like the above photoconductive layer.
The e-type photosensitive layer has a thickness in the range of 10 to 150 microns, preferably 50 to 120 microns. Further, as the second photoconductive layer, a photoconductive member is used which becomes a conductor with a portion of chromatic light in the visible light region under positive or negative charging or bipolar charging. In particular, materials that exhibit photoconductivity under bipolar charging include phthalocyanine pigments, organic pigments such as azo pigments, pyrylium dyes, and eutectic complexes and charge transfer complexes of these dyes and resins.

すなわち、第２光導電層は正または負のコロナ帯電を施
したときに電位保持能を有する素材で構成され且つ特定
波長の光で導体化する性質を有している。また、第２光
導電層は第２図に示すように単層であってもよいが特に
これに限定されるものではなく本発明の別の態様として
第３図に示すように電荷発生層６と電荷輸送層７の２層
にすることもできる。第２光導電層の膜厚は単層の場合
５〜６０μ程度が適切であり。That is, the second photoconductive layer is made of a material that has potential retention ability when subjected to positive or negative corona charging, and has the property of becoming a conductor with light of a specific wavelength. Further, the second photoconductive layer may be a single layer as shown in FIG. 2, but is not particularly limited to this, and as another embodiment of the present invention, as shown in FIG. It is also possible to have two layers, ie, a charge transport layer 7 and a charge transport layer 7. In the case of a single layer, the thickness of the second photoconductive layer is suitably about 5 to 60 μm.

２層の場合電荷発生層は０．１〜５μ程度そして電荷輸
送層は５〜５０μ程度が適切である。なお、本発明では
第１光導電層と第２光導電層との間に新たな層を設けて
電荷のリークを防止する等の機能向上を図ってもよい。In the case of two layers, it is appropriate that the charge generation layer has a thickness of about 0.1 to 5μ and the charge transport layer has a thickness of about 5 to 50μ. In the present invention, a new layer may be provided between the first photoconductive layer and the second photoconductive layer to improve functionality such as preventing charge leakage.

第２光導電層の形成にあたって結着剤を用いる場合には
その材料としては例えばポリエチレン、ポリスチレン、
ポリエステル、ポリアミド、ポリカーボネート、エポキ
シ、ウレタン、シリコーン、アルキッドなどの樹脂を用
いることができる。結着剤には可塑剤を併用できるが、
その添加量は結着剤に対し３層゛重量％ｉでが適当であ
る。可塑剤としてはジブチルフタレート、ジオクチルフ
タレートなどの一般に樹脂の可塑剤として用いられるも
のをそのまま使用できる。When a binder is used to form the second photoconductive layer, examples of the material include polyethylene, polystyrene,
Resins such as polyester, polyamide, polycarbonate, epoxy, urethane, silicone, and alkyd can be used. Plasticizers can be used together with binders, but
The appropriate amount of addition is 3 layers by weight % i based on the binder. As the plasticizer, those commonly used as plasticizers for resins, such as dibutyl phthalate and dioctyl phthalate, can be used as they are.

〔実施例〕〔Example〕

以下に比較例とともに実施例を掲げて本発明をさらに説
明するが本発明はこれに限定されるものではない。The present invention will be further explained below with reference to Examples along with Comparative Examples, but the present invention is not limited thereto.

実施例　１ 本発明品−１のＮ１−Ｂ中間層を設けたものと。Example 1 Inventive product-1 with N1-B intermediate layer provided.

従来のＮ１−Ｐ中間層を設けたもの（比較品Ａ−１）お
よび中間層のないもの（比較品Ｂ−１）の３種の試料を
作製し基体からのキャリヤの注入性を比較した。以下に
試料作製法と特性値を示す。Three types of samples were prepared, one with a conventional N1-P intermediate layer (comparative product A-1) and one without an intermediate layer (comparative product B-1), and the injectability of carriers from the substrate was compared. The sample preparation method and characteristic values are shown below.

本発明品−に表面が平滑なアルミニウム板をトリクレン
脱脂の後、ニッケルーホウ累無電解浴、　ＷＭＦ−１５
Ｐ　（ワールドメタルフイニツシーン′グ社製）にて約
１μの膜厚のＮ１およびＢをＡｌ板上に析出させた。得
られたＮ１−Ｂ膜を湯洗、乾燥の後３５０℃で６時間熱
処理した。この後、Ａｓ２Ｓｅ３光導電層を真空蒸着法
でＮｉ　−Ｂ中間層上に設は本発明品とした。蒸着条件
は、基板温度２００℃、真空度２〜５　Ｘ　１０−’　
Ｔｏｒｒ、ボート温度４７０℃、蒸着速度１μ７ｍｉ　
ｎおよび膜厚６０μとした。After degreasing an aluminum plate with a smooth surface using a nickel-boron electroless bath, WMF-15
N1 and B with a film thickness of about 1 μm were deposited on an Al plate using P (manufactured by World Metal Finishing Co., Ltd.). The obtained N1-B film was washed with hot water, dried, and then heat-treated at 350° C. for 6 hours. Thereafter, an As2Se3 photoconductive layer was formed on the Ni--B intermediate layer by vacuum evaporation to obtain a product of the present invention. The deposition conditions were: substrate temperature 200°C, degree of vacuum 2-5 x 10-'
Torr, boat temperature 470℃, deposition rate 1μ7mi
n and a film thickness of 60 μm.

比較品Ａ−に本発明品と同様なアルミニウム板をトリク
レン脱脂の後ニックルーリン無電解浴ブルーシューヌ−
（日本カニゼン製）にて約１μの膜厚のＮｉおよびＰを
Ａｌ板上に析出させ得られたＮ１−Ｐ膜を湯洗、乾燥の
後ろ５０℃で６時間熱処理した。その後、本発明品と全
く同様な方法でＡ３２Ｓｅ３光導電層を設は比較品Ａ−
ｉとした。For comparative product A-, an aluminum plate similar to the product of the present invention was degreased with trichlene and then soaked in a Nick Rulin electroless bath.
(manufactured by Nippon Kanigen) to precipitate Ni and P to a thickness of about 1 μm on an Al plate, and the resulting N1-P film was washed with hot water, dried, and then heat-treated at 50° C. for 6 hours. Thereafter, an A32Se3 photoconductive layer was formed on the comparative product A- in exactly the same manner as the present invention product.
It was set as i.

比較品Ｂ−に本発明品−１と同様なアルミニウム板をト
リクレン脱脂の後１本発明品−１と同様な方法でＡｌ板
上にＡｓ２８ｅ３光導電層を設は比較品Ｂ−１とした。Comparative product B- was prepared by using an aluminum plate similar to the present invention product-1 after degreasing with trichlene, and then forming an As28e3 photoconductive layer on the Al plate in the same manner as the present invention product-1.

以上のような方法で作製された本発明品および比較品の
正、負帯電電位をＥＰＡ　（川口電機製）にて測定した
。但し、正コロナ帯電を＋５ＫＶとし、負コロナ帯電を
一５ＫＶとした。測定結果を以下の表１に示す。The positive and negative charging potentials of the products of the present invention and comparative products produced by the method described above were measured using EPA (manufactured by Kawaguchi Electric). However, the positive corona charge was set to +5 KV, and the negative corona charge was set to -5 KV. The measurement results are shown in Table 1 below.

表　１ 上記の結果から、Ｎｉ　−Ｂ中間層を有する本発明品は
従来品（比較品）と比較して大巾に正孔の注入効率が改
善されていることがわかる。Table 1 From the above results, it can be seen that the product of the present invention having the Ni-B intermediate layer has greatly improved hole injection efficiency compared to the conventional product (comparative product).

実施例　２ 実施例１で作製した本発明品−１、比較品Ａ−１および
Ｂ−１ｔ−ニトロセルロース４ｔｔ脂（シャドー社製）
の１０重量パーセント溶液中に浸漬し各々のＡｓ２Ｓｅ
３第１光導亀層上にニトロセルロース樹脂からなる中間
層１μを形成した。その後真空蒸着法でこの中間層に５
ｅＴｅ第２光導電層用電荷発生層を形成した。蒸着条件
は合金組成８ｅＴｅ　８ｖｔ％、Ｃ１２５ｐｐｍ、基板
温度８０℃、真空度２〜５Ｘ　１０−６　Ｔｏｒｒ　、
ボート温度３２０℃、蒸着速度５　ｕ／ｍｉｎ、膜厚５
μとした。さらに５ｅＴｅ電荷発生層上にポリビニルカ
ルバゾールの５重量パーセント塩化メチレン溶液を塗布
乾燥して膜厚２０μの第２光導電層用電荷移動層を設は
複合感光体本発明品−２，比較品Ａ−２およびＢ−２を
得た。次にこれらの感光体に各々−５，７ＫＶの１次コ
ロナ帯電を行った後、＋　５．５　Ｋｖの２次コロナ帯
電を施し次いで■露光なし、■赤色フィルターを介した
露光、■白色露光を行い電位を測定したところ以下の表
２に示す結果を得た。Example 2 Invention product-1 produced in Example 1, comparative products A-1 and B-1 t-nitrocellulose 4tt fat (manufactured by Shadow Co., Ltd.)
Each As2Se was immersed in a 10 weight percent solution of
3. An intermediate layer of 1 μm made of nitrocellulose resin was formed on the first light guide layer. Afterwards, this intermediate layer is coated with 5
A charge generation layer for the eTe second photoconductive layer was formed. The deposition conditions were alloy composition 8eTe 8vt%, C125ppm, substrate temperature 80°C, degree of vacuum 2-5X 10-6 Torr,
Boat temperature: 320°C, deposition rate: 5 u/min, film thickness: 5
It was set to μ. Further, a 5% by weight methylene chloride solution of polyvinylcarbazole was applied and dried on the 5eTe charge generation layer to form a charge transfer layer for the second photoconductive layer with a film thickness of 20μ. 2 and B-2 were obtained. Next, each of these photoreceptors was subjected to a primary corona charge of -5.7 KV, and then a secondary corona charge of +5.5 Kv, and then subjected to three steps: (1) No exposure, (2) Exposure through a red filter, and (2) White exposure. When the potential was measured, the results shown in Table 2 below were obtained.

表　２ この表における本発明品と比較品間の赤色都電位差は実
施例１における負帯電電位差に相当することがわかる。Table 2 It can be seen that the difference in potential between the red dots between the inventive product and the comparative product in this table corresponds to the negative charging potential difference in Example 1.

従って本発明のＮ１−Ｂ中間層の介在により基体よシの
正孔の注入性が改善され２色カラー感光体の赤色部電位
の増加を図ることができたと判断できる。Therefore, it can be concluded that the presence of the N1-B intermediate layer of the present invention improves the hole injection properties of the substrate and makes it possible to increase the potential of the red portion of the two-color photoreceptor.

〔効　果〕〔effect〕

以上のようにして構成された本発明の電子写真感光体は
Ｎｉ　−Ｂ中間層の存在により光導電層の静電特性を損
うことなく基体からの正孔の注入効率を大巾に増加させ
ることができる。したがって、２色カラー複写用後合感
光体の要求特性を充分満足しまたＮ１−Ｂ中間層は既知
の無電解メッキ法によシ工業的に容易に成膜することが
できる。The electrophotographic photoreceptor of the present invention constructed as described above greatly increases the injection efficiency of holes from the substrate without impairing the electrostatic properties of the photoconductive layer due to the presence of the Ni-B intermediate layer. be able to. Therefore, the required characteristics of a post-mixing photoreceptor for two-color color copying are fully satisfied, and the N1-B intermediate layer can be easily formed industrially by the known electroless plating method.

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

第１図ないし第３図は本発明による電子写真感光体の層
構成例を示す断面図である。 １・・・導電性基体、２・・・Ｎ１−Ｂ中間層、３・・
・光導電層、４・・・第１光導電層、５・・・第２光導
電層、６・・・電荷発生層、７・・・電荷輸送層。 特許出願人　株式会社　リ　コ　−1 to 3 are cross-sectional views showing examples of the layer structure of an electrophotographic photoreceptor according to the present invention. DESCRIPTION OF SYMBOLS 1... Conductive substrate, 2... N1-B intermediate layer, 3...
- Photoconductive layer, 4... First photoconductive layer, 5... Second photoconductive layer, 6... Charge generation layer, 7... Charge transport layer. Patent applicant Rico Co., Ltd. −

Claims (1)

【特許請求の範囲】 １）　Ｎ１−Ｂ非晶質薄膜またはＮ１−Ｂ合金薄膜を被
覆した導電性基体表面に光導電層を設けたことを特徴と
する、電子写真感光体。 ２）　Ｎ１−Ｂ非晶質薄膜またはＮ１−Ｂ合金薄膜を被
覆した導電性基体表面に第１光導電層および第２光導電
層をこの順序で設けてなり、しかも前記第１光導電層が
少なくともその第２光導電層を透過する有彩色光に対し
感度を有しそして前記第２光導電層が可視光領域の一部
有彩色光に対し感度を有し且つ他の有彩色光を透過する
こと全特徴とする、電子写真感光体。 ３）前記第２光導電層が電荷発生層と電荷輸送層との２
層からなることを特徴とする特許許請求の範囲第２項記
載の電子写真感光体。[Scope of Claims] 1) An electrophotographic photoreceptor, characterized in that a photoconductive layer is provided on the surface of a conductive substrate coated with an N1-B amorphous thin film or an N1-B alloy thin film. 2) A first photoconductive layer and a second photoconductive layer are provided in this order on the surface of a conductive substrate coated with an N1-B amorphous thin film or an N1-B alloy thin film, and the first photoconductive layer is The second photoconductive layer is sensitive to at least chromatic light that passes through the second photoconductive layer, and the second photoconductive layer is sensitive to some chromatic light in the visible light range and transmits other chromatic light. An electrophotographic photoreceptor with all the following characteristics. 3) The second photoconductive layer includes a charge generation layer and a charge transport layer.
The electrophotographic photoreceptor according to claim 2, characterized in that it consists of a layer.