JPH08152728A - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
- Publication number
- JPH08152728A JPH08152728A JP6294114A JP29411494A JPH08152728A JP H08152728 A JPH08152728 A JP H08152728A JP 6294114 A JP6294114 A JP 6294114A JP 29411494 A JP29411494 A JP 29411494A JP H08152728 A JPH08152728 A JP H08152728A
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- charge
- general formula
- electrophotographic photoreceptor
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- group
- Prior art date
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- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電子写真用感光体の感光
層に係り、特に有機材料を含み電子写真方式のプリンタ
ー，複写機などに用いられる電子写真用感光体の酸化防
止剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive layer of an electrophotographic photoreceptor, and more particularly to an antioxidant for an electrophotographic photoreceptor which contains an organic material and is used in electrophotographic printers, copying machines and the like.
【０００２】[0002]
【従来の技術】電子写真用感光体は導電性基体上に光導
電性を有する感光層を積層した構造を採る。電荷の発生
や輸送を担う機能成分として有機化合物を含有する電子
写真用有機感光体、とりわけ材料の選択性が高く電荷発
生層、電荷輸送層などの機能層を積層してなる積層型電
子写真用有機感光体は機能設計が容易であり、塗工法に
よる生産性が高く、安全性に優れるなどの利点から複写
機をはじめとして各種プリンターへの応用が近年活発に
研究されている。2. Description of the Related Art An electrophotographic photosensitive member has a structure in which a photosensitive layer having photoconductivity is laminated on a conductive substrate. An organic electrophotographic photoreceptor for electrophotography, which contains an organic compound as a functional component responsible for charge generation and transport, especially for laminated electrophotography in which functional layers such as a charge generation layer and a charge transport layer are laminated with high material selectivity. Organic photoreceptors have been actively studied in recent years for application to various printers such as copying machines because of their advantages such as easy functional design, high productivity by coating method, and excellent safety.
【０００３】特に近年は、可とう性，熱安定性，膜形成
性などの利点を生かした有機材料を用いた感光体が実用
に供されている。さらには電荷発生物質としての新規ア
ゾ化合物や電荷輸送物質としての新規スチルベン誘導体
などが開発されて高感度化し、複写速度の速い複写機に
利用されている。In particular, in recent years, photoreceptors using organic materials have been put to practical use by taking advantage of advantages such as flexibility, thermal stability, and film forming property. Furthermore, a new azo compound as a charge generating substance and a new stilbene derivative as a charge transporting substance have been developed to have high sensitivity and are used in a copying machine having a high copying speed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、該積層
型有機感光体を実用条件で長時間使用すると、帯電電位
の低下、残留電位の上昇、感度の低下等の問題が発生す
る。これらの原因として、幾つかの外的要因を挙げるこ
とができる。即ち放電、帯電プロセスで発生するオゾン
に曝されること、そしてメンテナンス時に強力な外光に
曝されることなどである。これらの外的要因が上述諸特
性へ与える影響は該感光体をオゾン雰囲気中に放置する
か、或いは所定光量を照射するといった実験的方法で確
認できる。However, when the laminated organic photoreceptor is used for a long time under practical conditions, problems such as a decrease in charging potential, an increase in residual potential and a decrease in sensitivity occur. Some of these causes can be external factors. That is, it is exposed to ozone generated during discharge and charging processes, and exposed to strong external light during maintenance. The influence of these external factors on the above-mentioned various characteristics can be confirmed by an experimental method such as leaving the photoconductor in an ozone atmosphere or irradiating a predetermined amount of light.
【０００５】上述した問題を解決するべく、酸化防止剤
や紫外線吸収剤として知られている添加剤を感光層に含
有させるといった試みが種々なされているが、未だ全て
の要求性能を満足しうる技術は確立されていないのが現
状であった。本発明は上述の点に鑑みてなされその目的
は酸化防止剤の組み合わせを最適化してオゾンと外光に
対する安定化を図り、長期にわたり特性の安定した電子
写真用感光体を提供することにある。In order to solve the above-mentioned problems, various attempts have been made to incorporate an additive known as an antioxidant or an ultraviolet absorber into the photosensitive layer, but a technique capable of satisfying all required performances is still available. It was the current situation that has not been established. The present invention has been made in view of the above points, and an object thereof is to optimize the combination of antioxidants to stabilize ozone and external light, and to provide an electrophotographic photoreceptor having stable characteristics for a long period of time.
【０００６】[0006]
【課題を解決するための手段】上述の目的はこの発明に
よれば導電性基体上に感光層を有する電子写真用感光体
おいて、感光層中にフタロシアニンからなる電荷発生物
質、一般式〔Ｉａ〕または一般式〔Ｉｂ〕で示される化
合物の少なくとも一種からなる電荷輸送物質、一般式
〔II〕で示されるトコフェロール化合物の一種が少なく
とも含有される酸化防止剤の混合物を含むとすることに
より達成される。According to the present invention, in the electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, the above-mentioned object is to provide a charge-generating substance consisting of phthalocyanine in the photosensitive layer, represented by the general formula [Ia Or a charge-transporting substance comprising at least one compound represented by the general formula [Ib], and a mixture of antioxidants containing at least one tocopherol compound represented by the general formula [II]. It
【０００７】[0007]
【化７】 [Chemical 7]
【０００８】（一般式〔Ｉａ〕においてＲ1 , Ｒ2 , Ｒ
3 , Ｒ4 , Ｒ5 , Ｒ6 は置換または無置換のアリール
基，アルキル基またはアリレン基を表す。）(In the general formula [Ia], R 1 , R 2 , R
3 , R 4 , R 5 and R 6 represent a substituted or unsubstituted aryl group, alkyl group or arylene group. )
【０００９】[0009]
【化８】 Embedded image
【００１０】（一般式〔Ｉｂ〕においてＲ7 , Ｒ8 , Ｒ
9 は置換または無置換のアリール基，アルキル基またア
リレン基を表す。）(In the general formula [Ib], R 7 , R 8 and R
9 represents a substituted or unsubstituted aryl group, alkyl group or arylene group. )
【００１１】[0011]
【化９】 [Chemical 9]
【００１２】（一般式〔II〕においてＲ10 , Ｒ11 , Ｒ12
, Ｒ13 , Ｒ14は水素原子，水酸基，アミノ基またはアル
キル基を表す。） 上述の電子写真用感光体においてトコフェロール化合物
とともに用いられる酸化防止剤は構造式（III ―１）な
いし構造式（III ―３３）に示される化合物の少なくと
も一種であるとすることが有効である。(In the general formula [II], R 10 , R 11 and R 12
, R 13 and R 14 represent a hydrogen atom, a hydroxyl group, an amino group or an alkyl group. It is effective that the antioxidant used together with the tocopherol compound in the electrophotographic photoconductor is at least one of the compounds represented by the structural formulas (III-1) to (III-33).
【００１３】[0013]
【化１０】 [Chemical 10]
【００１４】[0014]
【化１１】 [Chemical 11]
【００１５】[0015]
【化１２】 [Chemical 12]
【００１６】[0016]
【作用】有機感光体において、感光層中にトコフェロー
ル化合物を含むと電荷輸送物質の酸化劣化，光劣化が防
止される。さらに他の酸化防止剤を添加することにより
これらの効果が増大する。In the organic photoreceptor, when the tocopherol compound is contained in the photosensitive layer, oxidative deterioration and photodegradation of the charge transport material are prevented. These effects are increased by adding another antioxidant.
【００１７】[0017]
【実施例】以下、本発明の実施例について、図面を参照
しながら説明する。図１はこの発明の実施例に係る正帯
電単層型電子写真用感光体を示す断面図である。図２は
この発明の実施例に係る負帯電積層型電子写真用感光体
を示す断面図である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view showing a positively charged single-layer type electrophotographic photoreceptor according to an embodiment of the present invention. FIG. 2 is a sectional view showing a negatively charged laminated electrophotographic photoreceptor according to an embodiment of the present invention.
【００１８】図３はこの発明の実施例に係る正帯電積層
型電子写真用感光体を示す断面図である。支持体である
導電性基体１としては、アルミニウム製円筒やアルミニ
ウム蒸着のフィルム等の導電性基体単独、あるいは該導
電性基体の表面をアルマイト化したもの、あるいは樹脂
皮膜などによる表面修飾を施したものが用いられる。本
実施例では該導電性基体としてアルミニウム製の肉厚１
ｍｍ、長さ３１０ｍｍ、外径６０ｍｍの円筒基体を洗
浄、乾燥したものを用いた。表面修飾に用いられる高分
子分散皮膜の材料としてはカゼイン、ポリビニルアルコ
ール、ナイロン、ポリアミド、メラニン、セルロースな
どの絶縁性高分子あるいはポリチオフェン、ポリピロー
ル、ポリアニリンなどの導電性高分子、あるいはこれら
高分子に金属酸化物粉末、低分子化合物を含有せしめた
ものが用いられる。FIG. 3 is a sectional view showing a positively charged laminated electrophotographic photoconductor according to an embodiment of the present invention. As the conductive substrate 1 which is a support, a conductive substrate such as an aluminum cylinder or an aluminum vapor-deposited film is used alone, or the surface of the conductive substrate is anodized, or the surface of which is modified with a resin film or the like. Is used. In this embodiment, the conductive substrate is made of aluminum and has a thickness of 1
A cylindrical substrate having a size of mm, a length of 310 mm, and an outer diameter of 60 mm was washed and dried. Materials for the polymer dispersion film used for surface modification include insulating polymers such as casein, polyvinyl alcohol, nylon, polyamide, melanin, and cellulose, or conductive polymers such as polythiophene, polypyrrole, and polyaniline, or metal for these polymers. An oxide powder or a material containing a low molecular weight compound is used.
【００１９】電荷輸送層６は、電荷輸送物質５とバイン
ダ樹脂により構成される。電荷輸送物質の具体例が化学
式（Ｉａ−１）ないし化学式（Ｉａ−３）または（Ｉｂ
−１）ないし化学式（Ｉｂ−５）に示される。これらの
誘導体も使用可能である。これらは組み合わせて用いる
ことができる。The charge transport layer 6 is composed of the charge transport material 5 and a binder resin. Specific examples of the charge transport material include chemical formulas (Ia-1) to (Ia-3) or (Ib).
-1) to chemical formula (Ib-5). These derivatives can also be used. These can be used in combination.
【００２０】[0020]
【化１３】 [Chemical 13]
【００２１】[0021]
【化１４】 Embedded image
【００２２】電荷輸送層６用の樹脂バインダとしては、
ポリカーボネート，ビスフェノールＡ型ポリカーボネー
ト，ビスフェノールＺ型ポリカーボネート，ビスフェノ
ールＡ型−ビフェニル共重合ポリカーボネート，ポリア
リレート等を用いることができるが、特にビスフェノー
ルＡ型−ビフェニル共重合ポリカーボネートを用いるこ
とにより、良好な特性が得られる。As the resin binder for the charge transport layer 6,
Polycarbonate, bisphenol A type polycarbonate, bisphenol Z type polycarbonate, bisphenol A type-biphenyl copolymerized polycarbonate, polyarylate and the like can be used, but particularly good properties can be obtained by using bisphenol A type-biphenyl copolymerized polycarbonate. To be
【００２３】また電荷輸送層６に添加する酸化防止剤の
具体例が化学式（II−１）ないし化学式（II−４）のト
コフェロール化合物に示される。トコフェロール化合物
と共に用いられる酸化防止剤がが化学式（III ―１）な
いし化学式（III −３３）に示される。Specific examples of the antioxidant added to the charge transport layer 6 are shown in the tocopherol compounds represented by the chemical formulas (II-1) to (II-4). The antioxidant used together with the tocopherol compound is represented by the chemical formula (III-1) to the chemical formula (III-33).
【００２４】[0024]
【化１５】 [Chemical 15]
【００２５】[0025]
【化１６】 Embedded image
【００２６】[0026]
【化１７】 [Chemical 17]
【００２７】[0027]
【化１８】 Embedded image
【００２８】被覆層７は暗所でコロナ放電の電荷を受容
して保持する機能を有しており、かつ電荷発生層が感応
する光を透過する性能を有し、露光により発生した電荷
発生層からの電荷の注入を受けて表面電荷が中和消滅さ
れることが必要である。被覆材料としては、ポリアミド
などの有機絶縁性皮膜形成材料、あるいはそれら有機材
料とＳｉＯ2 などの無機材料、さらには金属，金属酸化
物などの電気抵抗を低減せしめる材料とを混合して用い
ることもできる。The coating layer 7 has a function of receiving and holding a charge of corona discharge in a dark place, and also has a property of transmitting light which the charge generation layer is sensitive to, and the charge generation layer generated by exposure. It is necessary that the surface charge be neutralized and disappeared by receiving the charge injection from As the coating material, an organic insulating film forming material such as polyamide, or a mixture of these organic materials with an inorganic material such as SiO 2 or a material such as a metal or a metal oxide for reducing electric resistance may be used. it can.
【００２９】電荷発生層４は、電荷発生物質３とバイン
ダ樹脂により構成される。電荷発生物質の具体例が化学
式（IV―１）ないし化学式（IV―６）に示される。The charge generation layer 4 is composed of the charge generation substance 3 and a binder resin. Specific examples of the charge generating substance are shown in chemical formulas (IV-1) to (IV-6).
【００３０】[0030]
【化１９】 [Chemical 19]
【００３１】電荷発生層４用のバインダ樹脂としてはポ
リカーボネートポリエステル，ポリアミド，ポリウレタ
ン，エポキシポリビニルブチラール，ポリビニルアセタ
ール，フェノキシ樹脂，シリコーン樹脂，アクリル樹
脂，塩化ビニル樹脂，塩化ビニリデン樹脂，酢酸ビニル
樹脂，ホマール樹脂，セルロース樹脂，またはこれらの
共重合体，およびこれらのハロゲン化物，シアノエチル
化合物が用いられる。As the binder resin for the charge generation layer 4, polycarbonate polyester, polyamide, polyurethane, epoxy polyvinyl butyral, polyvinyl acetal, phenoxy resin, silicone resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, homer resin. , Cellulose resins, or copolymers thereof, and halides or cyanoethyl compounds thereof.
【００３２】正帯電単層型電子写真用感光体においては
電荷発生物質３と電荷輸送物質５とバインダ樹脂から感
光層２０が構成される。負帯電積層型電子写真用感光体
においては電荷輸送層６と電荷発生層４とから感光層２
１が構成される。正帯電積層型電子写真用感光体におい
ては電荷輸送層６と電荷発生層４とから感光層２２が構
成される。In the positively charged single layer type electrophotographic photoreceptor, the photosensitive layer 20 is composed of the charge generating substance 3, the charge transporting substance 5 and the binder resin. In the negative charging laminated type electrophotographic photoreceptor, the photosensitive layer 2 is composed of the charge transport layer 6 and the charge generating layer 4.
1 is configured. In the positively charged laminated electrophotographic photoreceptor, the photosensitive layer 22 is composed of the charge transport layer 6 and the charge generation layer 4.
【００３３】以下に負帯電型積層型感光体に適用した場
合について述べる。但し本実施例は本発明の請求範囲を
限定するものではない。The case where the invention is applied to a negative charging type laminated type photoreceptor will be described below. However, the present embodiment does not limit the scope of the claims of the present invention.
【００３４】[0034]
実施例 １ 数平均分子量１０万のポリアミド（商品名：Ｔ１７１，
（株）ダイセルーヒュルス製）４重量部とスチレン―マ
レイン酸樹脂（商品名：スプラパールAP,BASFJapan Lt
d. 製）１重量部をメタノール２００重量部と１ーブタ
ノール１００重量部との混合溶媒に溶解させ調製した樹
脂皮膜塗布液を用いて上述円筒基体上に樹脂皮膜0.1 μ
ｍをＤｉｐ法にて形成し、支持体である導電性基体１を
作製した。Example 1 Polyamide having a number average molecular weight of 100,000 (trade name: T171,
4 parts by weight of Daicel-Huls Co., Ltd. and styrene-maleic acid resin (trade name: Suprapearl AP, BASFJapan Lt
d. manufactured) 1 part by weight was dissolved in a mixed solvent of 200 parts by weight of methanol and 100 parts by weight of 1-butanol to prepare a resin film coating solution, and a resin film of 0.1 μ was formed on the cylindrical substrate.
m was formed by the Dip method to prepare the conductive substrate 1 as a support.
【００３５】電荷発生物質として化学式（IV―１) に示
した無金属フタロシアニン５重量部、バインダ樹脂とし
てポリビニルアセタール（商品名：エスレックスＫＳ―
１，積水化学工業）５重量部とをジクロロメタン７００
重量部と混合し、３時間混合機により混練を行い塗布液
を調製し電荷発生層用の塗液を作成した。電荷輸送物質
として化学式（Ｉａ―１）で示される化合物５００重量
部と化学式（１ｂ―１）で示される化合物５００重量部
を混合し、酸化防止剤として化学式( II−１）で示され
るトコフェロール化合物２０重量部、化学式（III ―３
１）で示される化合物５重量部、バインダ樹脂としてビ
スフェノールＡ型―ビフェニル共重合ポリカーボネート
（商品名ＢＰ−Ｐｃ：出光興産製、下記に構造式を示
す）１０００重量部とをジクロロメタン７０００重量部
に溶解し、電荷輸送層塗布液を調製した。5 parts by weight of the metal-free phthalocyanine represented by the chemical formula (IV-1) as the charge generating substance, and polyvinyl acetal as the binder resin (trade name: S-Rex KS-
1, Sekisui Chemical Co., Ltd.) and 5 parts by weight of dichloromethane 700
The coating liquid was prepared by mixing with 1 part by weight and kneading with a mixer for 3 hours to prepare a coating liquid for the charge generation layer. A tocopherol compound represented by the chemical formula (II-1) is mixed as an antioxidant by mixing 500 parts by weight of the compound represented by the chemical formula (Ia-1) and 500 parts by weight of the compound represented by the chemical formula (1b-1). 20 parts by weight, chemical formula (III-3
Dissolve 5 parts by weight of the compound represented by 1), 1000 parts by weight of bisphenol A type-biphenyl copolymerized polycarbonate (trade name BP-Pc: manufactured by Idemitsu Kosan, structural formula shown below) as a binder resin in 7,000 parts by weight of dichloromethane. Then, a charge transport layer coating solution was prepared.
【００３６】[0036]
【化２０】 Embedded image
【００３７】以上の塗布液を用いて上述支持体上に電荷
発生層、電荷輸送層を順次Ｄｉｐ法にて形成し、感光体
を作製した。 実施例 ２ 実施例１の化学式（Ｉａ―１）で示される電荷輸送物質
に替えて、化学式（Ｉａ―３）で示される電荷輸送物質
を用いる他は実施例１と同様にして感光体を作製した。 実施例 ３ 実施例１の化学式（Ｉｂ―１）で示される電荷輸送物質
に替えて、化学式（Ｉｂ―２）で示される電荷輸送物質
を用いる他は実施例１と同様にして感光体を作製した。 実施例 ４ 実施例１の化学式（II―１）で示されるトコフェロール
化合物に替えて、化学式（II―３）で示されるトコフェ
ロール化合物を用いる他は実施例１と同様にして感光体
を作製した。 実施例 ５ 実施例１の化学式（III ―３１）で示される酸化防止剤
に替えて、化学式（III ―１６）で示される酸化防止剤
を用いる他は実施例１と同様にして感光体を作製した。 実施例 ６ 実施例１の化学式（III ―３１）で示される酸化防止剤
に替えて、化学式（III ―２６）で示される酸化防止剤
を用いる他は実施例１と同様にして感光体を作製した。 実施例 ７ 実施例１のビスフェノールＡ型―ビフェニル共重合ポリ
カーボネートで示されるバインダ樹脂に替えてビスフェ
ノールＺ型ポリカーボネート（商品名 ＰＣＺ３００：
三菱瓦斯化学製）を用いる他は、実施例１と同様にして
感光体を作製した。 実施例 ８ 実施例１のビスフェノールＡ型―ビフェニル共重合ポリ
カーボネートで示されるバインダ樹脂に替えてビスフェ
ノールＡ型ポリカーボネート（商品名 パーンライトＬ
―１２２５：帝人化成製）を用いる他は、実施例１と同
様にして感光体を作製した。 比較例 １ 実施例１の化学式（II−１）に示されるトコフェロール
化合物と化学式（III―３１）で示される酸化防止剤を
配合しない他は実施例１と同様にして感光体を作製し
た。 比較例 ２ 実施例１の化学式（II−１）に示されるトコフェロール
化合物を配合しない他は実施例１と同様にして感光体を
作製した。 比較例 ３ 実施例１の化学式（III −３１）で示される酸化防止剤
を配合しない他は実施例１と同様にして感光体を作製し
た。 比較例 ４ 実施例２の化学式（II−１）に示されるトコフェロール
化合物を配合しない他は実施例２と同様にして感光体を
作製した。 比較例 ５ 実施例２の化学式（III −３１）で示される酸化防止剤
を配合しない他は実施例２と同様にして感光体を作製し
た。 比較例 ６ 実施例７の化学式（II−１）に示されるトコフェロール
化合物を配合しない他は実施例７と同様にして感光体を
作製した。 比較例 ７ 実施例８の化学式（III −３１）で示される酸化防止剤
を配合しない他は実施例８と同様にして感光体を作製し
た。A charge-generating layer and a charge-transporting layer were sequentially formed on the above-mentioned support by the Dip method using the above coating solution to prepare a photoreceptor. Example 2 A photoreceptor was prepared in the same manner as in Example 1 except that the charge transporting material represented by the chemical formula (Ia-1) in Example 1 was replaced by the charge transporting material represented by the chemical formula (Ia-3). did. Example 3 A photoconductor was prepared in the same manner as in Example 1 except that the charge transporting material represented by the chemical formula (Ib-1) in Example 1 was replaced by the charge transporting material represented by the chemical formula (Ib-2). did. Example 4 A photoconductor was produced in the same manner as in Example 1 except that the tocopherol compound represented by the chemical formula (II-1) in Example 1 was replaced with the tocopherol compound represented by the chemical formula (II-3). Example 5 A photoreceptor was prepared in the same manner as in Example 1 except that the antioxidant represented by the chemical formula (III-16) in Example 1 was used instead of the antioxidant represented by the chemical formula (III-31). did. Example 6 A photoconductor is produced in the same manner as in Example 1 except that the antioxidant represented by the chemical formula (III-26) is used instead of the antioxidant represented by the chemical formula (III-31) in Example 1. did. Example 7 Instead of the binder resin represented by the bisphenol A type-biphenyl copolymer polycarbonate of Example 1, a bisphenol Z type polycarbonate (trade name PCZ300:
A photoconductor was prepared in the same manner as in Example 1 except that Mitsubishi Gas Chemical Co., Ltd.) was used. Example 8 In place of the binder resin represented by the bisphenol A-biphenyl copolycarbonate of Example 1, a bisphenol A type polycarbonate (trade name Panelite L
-1225: manufactured by Teijin Kasei Co., Ltd., and a photoconductor was manufactured in the same manner as in Example 1. Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the tocopherol compound represented by the chemical formula (II-1) and the antioxidant represented by the chemical formula (III-31) were not blended. Comparative Example 2 A photoconductor was produced in the same manner as in Example 1 except that the tocopherol compound represented by the chemical formula (II-1) of Example 1 was not blended. Comparative Example 3 A photoconductor was prepared in the same manner as in Example 1 except that the antioxidant represented by the chemical formula (III-31) in Example 1 was not added. Comparative Example 4 A photoconductor was produced in the same manner as in Example 2 except that the tocopherol compound represented by the chemical formula (II-1) of Example 2 was not added. Comparative Example 5 A photoconductor was prepared in the same manner as in Example 2 except that the antioxidant represented by the chemical formula (III-31) of Example 2 was not added. Comparative Example 6 A photoconductor was produced in the same manner as in Example 7 except that the tocopherol compound represented by the chemical formula (II-1) of Example 7 was not blended. Comparative Example 7 A photoconductor was produced in the same manner as in Example 8 except that the antioxidant represented by the chemical formula (III-31) of Example 8 was not added.
【００３８】上述実施例と比較例で作製した感光体の電
子写真特性を評価した。連続使用時における電位変動を
評価する目的で、帯電機構・露光機構・除電機構の出力
を固定した複写機に各種感光体を搭載し、常温常湿（２
０℃，６０ＲＨ）の雰囲気でＡ３用紙５万枚のランニン
グ試験を行いランニング開始時の白紙電位（Ｖｗ）と黒
紙電位（Ｖｂ）を測定、ランニング終了時の各電位変化
量（ΔＶｗ，ΔＶｂ）を得た。さらに耐オゾン性を評価
する目的で各感光体をオゾン濃度１００ｐｐｍの環境下
に４時間暴露し、暴露前後の半減露光量を測定、比較し
た。The electrophotographic characteristics of the photoconductors produced in the above-mentioned Examples and Comparative Examples were evaluated. For the purpose of evaluating potential fluctuations during continuous use, various photoconductors were mounted on a copying machine with fixed outputs of the charging mechanism, exposure mechanism, and static elimination mechanism, and the temperature and humidity (2
A running test of 50,000 A3 sheets is performed in an atmosphere of 0 ° C. and 60 RH, and the white paper potential (Vw) and the black paper potential (Vb) at the start of running are measured, and the potential changes at the end of running (ΔVw, ΔVb) Got Further, for the purpose of evaluating ozone resistance, each photoconductor was exposed to an environment having an ozone concentration of 100 ppm for 4 hours, and the half-exposure amount before and after the exposure was measured and compared.
【００３９】さらに耐強光疲労性を評価する目的で各感
光体に１０００ルクスの光を１時間照射し、一定帯電条
件下での照射前の初期帯電電位（Ｖｓ）を測定、照射終
了後の帯電電位変化量（ΔＶｓ）を得た。これらの結果
を表１に示す。Further, for the purpose of evaluating the high light fatigue resistance, each photoconductor was irradiated with light of 1000 lux for 1 hour, and the initial charging potential (Vs) before irradiation under a constant charging condition was measured. The amount of change in charging potential (ΔVs) was obtained. Table 1 shows the results.
【００４０】[0040]
【表１】 [Table 1]
【００４１】上述の結果から明らかなように、感光層に
トコフェロール化合物と他の酸化防止剤を含まない感光
体は、オゾン暴露あるいは強光照射によって感光体特性
が低下し実機でのランニング試験による電位変動は実用
の範囲から逸脱している。また実施例１，７，８の結果
からわかるようにバインダ樹脂としてビスフェノールＡ
型―ビフェニル共重合ポリカーボネートを使用すると卓
越した安定性が得られる。As is clear from the above results, the photoreceptor containing no tocopherol compound and other antioxidants in the photosensitive layer deteriorates in photoreceptor characteristics due to exposure to ozone or strong light, and the potential in a running test in an actual machine is decreased. The variation deviates from the practical range. As can be seen from the results of Examples 1, 7, and 8, bisphenol A was used as the binder resin.
Excellent stability is obtained using the type-biphenyl copolycarbonate.
【００４２】[0042]
【発明の効果】この発明によれば感光層中にフタロシア
ニンからなる電荷発生物質、一般式〔Ｉａ〕または一般
式〔Ｉｂ〕で示される化合物の少なくとも一種からなる
電荷輸送物質、一般式〔II〕で示されるトコフェロール
化合物の一種が少なくとも含有される酸化防止剤の混合
物を含むので、電子写真用感光体を使用する際に発生す
るオゾンあるいは強光照射によって特性の変化がなく連
続使用における特性の安定性に優れる電子写真用感光体
が得られる。According to the present invention, a charge generating substance comprising phthalocyanine in the photosensitive layer, a charge transporting substance comprising at least one compound represented by the general formula [Ia] or the general formula [Ib], and the general formula [II]. Since it contains a mixture of antioxidants containing at least one of the tocopherol compounds shown in Fig. 3, there is no change in the characteristics due to ozone or strong light irradiation generated when the electrophotographic photoreceptor is used, and the stability of the characteristics in continuous use is obtained. An electrophotographic photoreceptor having excellent properties is obtained.
【図１】この発明の実施例に係る正帯電単層型電子写真
用感光体を示す断面図FIG. 1 is a cross-sectional view showing a positively charged single-layer type electrophotographic photoconductor according to an embodiment of the present invention.
【図２】この発明の実施例に係る負帯電積層型電子写真
用感光体を示す断面図FIG. 2 is a cross-sectional view showing a negatively charged laminated electrophotographic photoconductor according to an embodiment of the present invention.
【図３】この発明の実施例に係る正帯電積層型電子写真
用感光体を示す断面図FIG. 3 is a cross-sectional view showing a positively charged laminated electrophotographic photoreceptor according to an embodiment of the present invention.
１ 導電性基体 ３ 電荷発生物質 ４ 電荷発生層 ５ 電荷輸送物質 ６ 電荷輸送層 ７ 被覆層 ２０ 感光層 ２１ 感光層 ２２ 感光層 1 Conductive Substrate 3 Charge Generating Material 4 Charge Generating Layer 5 Charge Transporting Material 6 Charge Transporting Layer 7 Covering Layer 20 Photosensitive Layer 21 Photosensitive Layer 22 Photosensitive Layer
Claims (2)
感光体おいて、感光層中にフタロシアニンからなる電荷
発生物質、一般式〔Ｉａ〕または一般式〔Ｉｂ〕で示さ
れる化合物の少なくとも一種からなる電荷輸送物質、一
般式〔II〕で示されるトコフェロール化合物の一種が少
なくとも含有される酸化防止剤の混合物を含むことを特
徴とする電子写真用感光体。 【化１】 （一般式〔Ｉａ〕においてＲ1 , Ｒ2 , Ｒ3 , Ｒ4 , Ｒ
5 , Ｒ6 は置換または無置換のアリール基，アルキル基
またはアリレン基を表す。） 【化２】 （一般式〔Ｉｂ〕においてＲ7 , Ｒ8 , Ｒ9 は置換また
は無置換のアリール基，アルキル基またアリレン基を表
す。） 【化３】 （一般式〔II〕においてＲ10 , Ｒ11 , Ｒ12 , Ｒ13 , Ｒ14
は水素原子，水酸基，アミノ基またはアルキル基を表
す。）1. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein at least a charge-generating substance consisting of phthalocyanine, a compound represented by the general formula [Ia] or the general formula [Ib] is contained in the photosensitive layer. An electrophotographic photoreceptor comprising a mixture of an antioxidant containing at least one charge-transporting substance and one of the tocopherol compounds represented by the general formula [II]. Embedded image (In the general formula [Ia], R 1 , R 2 , R 3 , R 4 , R
5 and R 6 represent a substituted or unsubstituted aryl group, alkyl group or arylene group. ) (In the general formula [Ib], R 7 , R 8 and R 9 represent a substituted or unsubstituted aryl group, alkyl group or arylene group.) (In the general formula [II], R 10 , R 11 , R 12 , R 13 , R 14
Represents a hydrogen atom, a hydroxyl group, an amino group or an alkyl group. )
て、トコフェロール化合物とともに用いられる酸化防止
剤は構造式（III ―１）ないし構造式（III ―３３）に
示される化合物の少なくとも一種であることを特徴とす
る電子写真用感光体 【化４】 【化５】 【化６】 2. The electrophotographic photosensitive member according to claim 1, wherein the antioxidant used together with the tocopherol compound is at least one compound represented by structural formula (III-1) to structural formula (III-33). Electrophotographic photoconductor characterized by the following: Embedded image [Chemical 6]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29411494A JP3265870B2 (en) | 1994-11-29 | 1994-11-29 | Electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29411494A JP3265870B2 (en) | 1994-11-29 | 1994-11-29 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08152728A true JPH08152728A (en) | 1996-06-11 |
| JP3265870B2 JP3265870B2 (en) | 2002-03-18 |
Family
ID=17803476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29411494A Expired - Fee Related JP3265870B2 (en) | 1994-11-29 | 1994-11-29 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3265870B2 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP3265870B2 (en) | 2002-03-18 |
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