JPH06222588A - Image forming apparatus - Google Patents

Image forming apparatus

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Publication number
JPH06222588A
JPH06222588A JP856693A JP856693A JPH06222588A JP H06222588 A JPH06222588 A JP H06222588A JP 856693 A JP856693 A JP 856693A JP 856693 A JP856693 A JP 856693A JP H06222588 A JPH06222588 A JP H06222588A
Authority
JP
Japan
Prior art keywords
substituted
group
optionally substituted
image forming
forming apparatus
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
JP856693A
Other languages
Japanese (ja)
Inventor
Katsumi Matsuura
克巳 松浦
Masanari Asano
真生 浅野
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.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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 Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP856693A priority Critical patent/JPH06222588A/en
Publication of JPH06222588A publication Critical patent/JPH06222588A/en
Pending legal-status Critical Current

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  • Photoreceptors In Electrophotography (AREA)

Abstract

PURPOSE:To always stably obtain high-quality images small in deterioration due to fatigue at the time of repeatingly forming images for a long period by incorporating a specified compound as an electric charge transfer material in the uppermost layer of an electrophotographic sensitive body. CONSTITUTION:The image forming apparatus comprises at least the electrophotographic sensitive body and each means of charging, exposure, development, transfer, and cleaning in its outer circumference. An ozone concentration in the apparatus is <=0.5ppm and the uppermost layer of the photosensitive body is the charge transfer layer having an oxygen gas permeability coefficient of <=1.0X10<-7> (cc/cm<2>.S.cmHg) per unit area, and containing as the charge transfer material a compound represented by formula I or II in which each of Ar1 and Ar2 is an optionally substituted phenyl; Ar3 is an optionally substituted arylene; Ar4 is an optionally substituted aryl or the like; each of Ar5-Ar7 is an optionally substituted aryl or such heterocyclic group, or the like; each of R1 and R2 is H, an optionally substituted aryl or the like; and Ar8 is an optionally substituted arylene.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明はオゾン対策が施されて繰
返し像形成の過程で疲労劣化がなく安定した画像形成が
可能な画像形成装置に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus capable of stable image formation without fatigue deterioration during repeated image formation by taking measures against ozone.

【0002】[0002]

【従来の技術】従来、カールソン法に基づく電子写真に
おいては感光体表面を一様に帯電し、像様に露光して静
電潜像を形成し、該静電潜像を現像してトナー像を形成
し、該トナー像を転写材上に転写・定着して像形成が行
われる。転写後の感光体は残留トナーの除去及び除電が
行われて長期に亘り反復使用される。
2. Description of the Related Art Conventionally, in electrophotography based on the Carlson method, the surface of a photoconductor is uniformly charged, imagewise exposed to form an electrostatic latent image, and the electrostatic latent image is developed to form a toner image. Is formed, and the toner image is transferred and fixed on a transfer material to form an image. After the transfer, the photosensitive member is removed of residual toner and discharged, and is repeatedly used for a long time.

【0003】従って感光体としては、帯電特性、感度特
性及び残留電位特性等の電子写真特性の外、長期に亘る
繰返し像形成に耐える高耐久性が要請される。
Therefore, the photoreceptor is required to have high durability to withstand repeated image formation over a long period of time, in addition to electrophotographic characteristics such as charging characteristics, sensitivity characteristics and residual potential characteristics.

【0004】ところで近年無害で低コストであり、加工
性に優れ、用途に応じて選択の自由度大なる有機光導電
性物質を用いた有機感光体が注目されるようになり、特
に電荷発生機能を電荷発生物質(CGM)に電荷輸送機
能を電荷輸送物質(CTM)に分担させた機能分離型の
有機感光体が研究、開発されている。
By the way, in recent years, an organic photoconductor using an organic photoconductive substance, which is harmless, low in cost, excellent in processability, and has a high degree of freedom in selection according to the use, has attracted attention, and particularly has a charge generating function. There has been studied and developed a function-separated type organic photoconductor in which a charge generation material (CGM) and a charge transport material (CTM) share the charge transfer function.

【0005】なお前記機能分離型の有機感光体として
は、優れた特性を有するホール輸送性のP型CTMが多
数見出されていることから、CGMを含有する電荷発生
層(CGL)を下層とし、CTMを含有する電荷輸送層
(CTL)を上層とするものが主流とされている。
Since many hole-transporting P-type CTMs having excellent properties have been found as the above-mentioned function-separated type organic photoconductor, the charge generation layer (CGL) containing CGM is used as the lower layer. , A CTM-containing charge transport layer (CTL) as an upper layer is mainly used.

【0006】ここで前記有機感光体の研究、開発に当
り、帯電または転写用のコロナ放電器から発生するオゾ
ンはCTM、特に電子写真特性に優れたCTMを破壊し
て感光層を劣化させる外、人体にも有害であることから
オゾン対策が重要な課題となっている。
Here, in the research and development of the above-mentioned organic photoreceptor, ozone generated from a corona discharger for charging or transferring destroys CTM, particularly CTM excellent in electrophotographic characteristics and deteriorates the photosensitive layer. Countermeasures against ozone have become an important issue because they are harmful to the human body.

【0007】前記有機感光体のCTMとしては、例えば
特開昭61-48869号に記載されるように、スチリル系化合
物、ヒドラゾン系化合物、ピラゾリン系化合物、トリア
リールアミン系化合物等が知られているが、これらは必
ずしもセレン系感光体に匹敵する感光体をうるためのC
TMとして十分とは言えない。そこで例えば特開昭58-6
5440号、特開平1-93746号には前記高感度特性を与える
CTMとして特定構造のスチリル誘導体が提案されてい
る。
As the CTM for the organic photoconductor, for example, styryl compounds, hydrazone compounds, pyrazoline compounds, triarylamine compounds, etc. are known as described in JP-A-61-48869. However, these are not necessarily C for obtaining a photoconductor comparable to the selenium photoconductor.
Not enough as a TM. Then, for example, JP-A-58-6
5440 and JP-A-1-93746 propose a styryl derivative having a specific structure as a CTM which gives the above-mentioned high sensitivity characteristics.

【0008】[0008]

【発明が解決しようとする問題点】しかしながら前記特
定構造のスチリル誘導体及びから成るCTMはコロナ放
電により発生するオゾンに対して極めて弱く、該CTM
を含有するCTLを表面層とする感光体は反復像形成を
行なうと、前記オゾンにより疲労劣化して電子写真性能
が著しく低下するという問題がある。
However, the CTM composed of the styryl derivative and the specific structure is extremely weak against ozone generated by corona discharge, and the CTM is
When a photoreceptor having CTLs containing CTL as a surface layer is subjected to repeated image formation, there is a problem that fatigue is deteriorated by the ozone and the electrophotographic performance is significantly deteriorated.

【0009】以上の例の如く、感度その他電子写真特性
に優れたCTMを開発したとしても、そのようなCTM
を用いた感光体は繰返し像形成の過程でオゾン等により
劣化を受け、その性能が半減すると云う問題があり、そ
れだけCTMの選択の自由が失われ、望ましい電子写真
性能を有する感光体をうることが困難になる。
As described above, even if a CTM having excellent sensitivity and other electrophotographic characteristics is developed, such a CTM
There is a problem in that the photoconductor using is deteriorated by ozone or the like in the process of repeatedly forming an image and its performance is halved, so that the freedom of selection of CTM is lost and a photoconductor having desirable electrophotographic performance is obtained. Becomes difficult.

【0010】一方画像形成装置において、オゾンの発生
を少なくするため種々の試みがなされている。例えば帯
電または転写において、放電ワイヤによるコロナ放電方
式に代えてバイアス電圧が印加された導電ローラを用い
る接触方式が注目されている。このような接触方式とす
ることにより画像形成装置内のオゾンの発生量は減少す
るが、感光体の一層の高耐久性化が要請され、これに対
しては、画像形成装置内のオゾンの発生および作用の反
応論的対策のみでは不十分である。
On the other hand, various attempts have been made to reduce the generation of ozone in the image forming apparatus. For example, in charging or transfer, a contact method using a conductive roller to which a bias voltage is applied has attracted attention instead of the corona discharge method using a discharge wire. Although the amount of ozone generated in the image forming apparatus is reduced by adopting such a contact method, it is required to further enhance the durability of the photoconductor. And responsive measures of action alone are not sufficient.

【0011】本発明者の鋭意検討の結果、前記のように
電子写真性能、特に感度特性に優れてはいるが、オゾン
劣化の大きいCTMを表面層に有する感光体を画像形成
装置に組込み、多数回に亘る繰返し像形成を行い安定し
て高画質をうるためには、装置内のオゾン濃度をある限
度内に抑制すると共に、これと組合せて、感光層自体の
物性を改良する必要がある。
As a result of intensive study by the present inventors, as described above, a large number of photoconductors having a CTM having a large ozone deterioration as a surface layer, which are excellent in electrophotographic performance, are incorporated in an image forming apparatus. In order to form images repeatedly over a number of times and to stably obtain high image quality, it is necessary to suppress the ozone concentration in the apparatus within a certain limit and improve the physical properties of the photosensitive layer itself in combination with this.

【0012】[0012]

【発明の目的】本発明の目的は、電子写真特性に優れて
いて、特に高感度特性を有する感光体が組込まれた画像
形成装置であって、該装置を用いて長期に亘り繰返し像
形成を行なったとき、疲労劣化が少なく終始安定して高
画質が得られる画像形成装置を提供することにある。
It is an object of the present invention to provide an image forming apparatus incorporating a photoconductor having excellent electrophotographic characteristics, and particularly having high sensitivity characteristics, which can be used for repeated image formation over a long period of time. An object of the present invention is to provide an image forming apparatus capable of stably obtaining high image quality with little fatigue deterioration when performed.

【0013】[0013]

【発明の構成】前記の目的は、少くとも電子写真感光体
と該感光体の外周に帯電、露光、現像、転写及びクリー
ニングの各手段を有する画像形成装置において、該装置
内のオゾン濃度が0.5ppm以下であり、且つ前記感光体の
最上層がCTMとして前記[化1]に記載の構成諸元を特
定した一般式〔I〕または〔II〕で示される化合物を含
有する電荷輸送層(CTL)で構成され、該電荷輸送層
(CTL)の単位膜厚当りの酸素ガス透過係数が1.0×1
0-7(cc/cm2・S・cmHg)以下であることを特徴とする画像
形成装置により達成される。
SUMMARY OF THE INVENTION The above object is to provide an image forming apparatus having at least an electrophotographic photosensitive member and means for charging, exposing, developing, transferring and cleaning the outer periphery of the photosensitive member, and the ozone concentration in the apparatus is 0.5. A charge transport layer (CTL) containing a compound represented by the general formula [I] or [II], which has a ppm or less and the uppermost layer of the photoreceptor is CTM and has the structural specifications described in [Chemical Formula 1] specified. ), And the oxygen gas permeation coefficient per unit film thickness of the charge transport layer (CTL) is 1.0 × 1.
It is achieved by an image forming apparatus characterized by being 0 −7 (cc / cm 2 · S · cmHg) or less.

【0014】一般式〔I〕において、Ar4に対する置換
基としてアルキル基、アルコキシ基、アリールオキシ
基、水酸基、ハロゲン原子よりなる群より1つ以上の組
合せで用いられる。
In the general formula [I], a substituent for Ar 4 is used in a combination of at least one selected from the group consisting of an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group and a halogen atom.

【0015】Ar1,Ar2,Ar3の好ましい置換基として
はハロゲン原子、置換,非置換のアルキル基、アルコキ
シ基、置換,非置換のアミノ基、水酸基、アリールオキ
シ基である。
Preferred substituents for Ar 1 , Ar 2 and Ar 3 are a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted amino group, a hydroxyl group or an aryloxy group.

【0016】また一般式〔II〕において、Ar5,Ar6
Ar7の表すアリール基、芳香族置換アルキル基及び複素
環は、好ましくは置換,非置換のフェニル基、ナフチル
基であり、Ar8の表すアリーレン基は、好ましくは置
換,非置換のフェニレン基、置換,非置換のナフチレン
基である。R1,R2の表すアルキル基、アリール基は、
好ましくは炭素原子数が1個から8個のアルキル基、置
換,非置換のフェニル基、置換,非置換のナフチル基で
ある。
In the general formula [II], Ar 5 , Ar 6 ,
The aryl group, aromatic substituted alkyl group and heterocycle represented by Ar 7 are preferably substituted and unsubstituted phenyl groups and naphthyl groups, and the arylene group represented by Ar 8 is preferably substituted and unsubstituted phenylene groups, It is a substituted or unsubstituted naphthylene group. The alkyl group and aryl group represented by R 1 and R 2 are
Preferred is an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

【0017】即ち本発明においては、前記一般式
〔I〕,〔II〕で示される化合物のキャリア輸送能を活
用し、これをキャリアの発生と輸送とをそれぞれ別個の
物質で行ういわゆる機能分離型電子写真感光体のキャリ
ア輸送物質として用いることにより、被膜物性に優れ、
電荷保持力、感度、残留電位等の電子写真特性に優れ、
かつ繰返し使用に供したときにも疲労劣化が少ない安定
した特性を発揮し得る電子写真感光体を作成することが
できる。
That is, in the present invention, the so-called function-separated type in which the carrier transporting ability of the compounds represented by the above-mentioned general formulas [I] and [II] is utilized and the carrier generation and the transport are performed by separate substances, respectively. By using it as a carrier transporting material for electrophotographic photoreceptors, it has excellent coating physical properties,
Excellent electrophotographic properties such as charge retention, sensitivity, residual potential,
In addition, it is possible to prepare an electrophotographic photosensitive member which can exhibit stable characteristics with little fatigue deterioration even when repeatedly used.

【0018】また本発明で用いられるキャリア輸送物質
は前記一般式〔I〕,〔II〕で示される夫々の化合物の
中から夫々少なくとも1種の組合せで併用することがで
きる。また他のキャリア輸送物質を加え合わせ使用して
もよい。
The carrier transport material used in the present invention can be used in combination of at least one compound selected from the compounds represented by the above formulas [I] and [II]. Further, other carrier transport substances may be added and used.

【0019】前記併用する重量比〔I〕/〔II〕は3/
97〜97/3、好ましくは5/95〜50/50である。
The weight ratio [I] / [II] used in combination is 3 /
It is 97 to 97/3, preferably 5/95 to 50/50.

【0020】前記一般式〔I〕で示される本発明に有効
なキャリア輸送物質の具体例としては、例えば次の構造
式を有するものが挙げられる。
Specific examples of the carrier-transporting substance represented by the above general formula [I] effective in the present invention include those having the following structural formulas.

【0021】[0021]

【化2】 [Chemical 2]

【0022】[0022]

【化3】 [Chemical 3]

【0023】[0023]

【化4】 [Chemical 4]

【0024】[0024]

【化5】 [Chemical 5]

【0025】[0025]

【化6】 [Chemical 6]

【0026】以上のようなトリアリールアミン誘導体
は、公知の方法により容易に合成することができる。例
えばOrganic Reactions vol.25 p.73(John Wiley & Son
s,Inc。)記載の如く、下記一般式〔A〕で示される芳香
族アルデヒドと下記一般式〔B〕で示されるホスホン酸
ジアルキルとをN,N-ジメチルホルムアミド等の溶媒中ナ
トリウムアルコキサイド、ナトリウムハイドライド等の
塩基の存在下縮合することによって容易に得ることがで
きる。
The above triarylamine derivative can be easily synthesized by a known method. For example, Organic Reactions vol.25 p.73 (John Wiley & Son
s, Inc. As described above, an aromatic aldehyde represented by the following general formula [A] and a dialkyl phosphonate represented by the following general formula [B] are treated with sodium alkoxide, sodium hydride, etc. in a solvent such as N, N-dimethylformamide. It can be easily obtained by condensation in the presence of a base.

【0027】[0027]

【化7】 [Chemical 7]

【0028】ここでAr1,Ar2,Ar3,Ar4は一般式
〔I〕と同じものを表し、R′はアルキル基、アリール
基を表す。
Here, Ar 1 , Ar 2 , Ar 3 and Ar 4 are the same as those in the general formula [I], and R'is an alkyl group or an aryl group.

【0029】次に一般式〔II〕で示されるキャリア輸送
物質の具体例としては、下記の構造式を有するスチル化
合物が挙げられる。
Next, specific examples of the carrier transporting material represented by the general formula [II] include still compounds having the following structural formulas.

【0030】[0030]

【化8】 [Chemical 8]

【0031】[0031]

【化9】 [Chemical 9]

【0032】[0032]

【化10】 [Chemical 10]

【0033】[0033]

【化11】 [Chemical 11]

【0034】[0034]

【化12】 [Chemical 12]

【0035】[0035]

【化13】 [Chemical 13]

【0036】[0036]

【化14】 [Chemical 14]

【0037】前記一般式〔II〕で示されるスチル化合物
は特開昭58-58550号、同58-65440号、同58-198043号等
の公知の合成法により調製することができる。
The still compound represented by the general formula [II] can be prepared by a known synthesis method such as JP-A-58-58550, JP-A-58-65440 and JP-A-58-198043.

【0038】本発明の感光体は図1に示すように導電性
支持体1上に必要により中間層2を設け、該中間層2上
にCGL3,CTL4をこの順に設けた構成とされる。
即ち、導電性支持体上に支持体1からの電荷注入を阻止
し、CGLとの接着を目的として、例えばアルキル化ナ
イロン、アルコキシ化ナイロン、塩ビ-酢ビ共重合樹
脂、塩ビ-酢ビ-無水マレイン酢共重合樹脂、その他のポ
リビニルアルコール、エチルセルロース、カルボキシメ
チルセルロース、カゼイン、澱粉等の有機高分子化合物
をディップ塗布、スプレィ塗布等の方法により、また、
酸化アルミニウム等を真空蒸着、スパッタリング等の方
法等により0.01〜2μm厚の中間層2を形成する。
As shown in FIG. 1, the photoreceptor of the present invention has a structure in which an intermediate layer 2 is provided on a conductive support 1 if necessary, and CGL3 and CTL4 are provided on the intermediate layer 2 in this order.
That is, for the purpose of preventing charge injection from the support 1 on the conductive support and adhering to CGL, for example, alkylated nylon, alkoxylated nylon, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-anhydrous. Malein vinegar copolymer resin, other polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, casein, organic polymer compounds such as starch by dip coating, spray coating, etc.,
The intermediate layer 2 having a thickness of 0.01 to 2 μm is formed by a method such as vacuum deposition or sputtering of aluminum oxide or the like.

【0039】次いで該中間層2上にバインダ樹脂100重
量部に対してCGM5〜500重量部、好ましくは20〜300
重量部、必要によりCTM10〜200重量部相溶して含有
する0.05〜10μm厚のCGL3を形成する。
Then, on the intermediate layer 2, 5 to 500 parts by weight, preferably 20 to 300 parts by weight of CGM is added to 100 parts by weight of the binder resin.
CGL3 having a thickness of 0.05 to 10 .mu.m is formed by compatibilizing CTM in an amount of 10 to 200 parts by weight.

【0040】次いで該CGL3上にバインダ樹脂100重
量部に対してCTMを20〜200重量部、好ましくは30〜1
00重量部相溶して含有する5〜50μm厚のCTL4を形
成して感光体をうる。
Then, 20 to 200 parts by weight, preferably 30 to 1 part by weight of CTM is added to 100 parts by weight of the binder resin on the CGL3.
A photosensitive member is obtained by forming CTL4 having a thickness of 5 to 50 μm, which is contained by compatibilizing with 00 parts by weight.

【0041】前記CGLに含有されるCGMとしては、
特に限定はないが、下記化合物が挙げられる。
The CGM contained in the CGL is
Although not particularly limited, the following compounds may be mentioned.

【0042】(1)モノアゾ顔料、ポリアゾ顔料、金属
錯塩アゾ顔料、ピラゾロンアゾ顔料、スチルベンアゾ顔
料及びチアゾールアゾ顔料等のアゾ系顔料 (2)ペリレン酸無水物及びペリレン酸イミド等のペリ
レン系顔料 (3)アントラキノン誘導体、アントアントロン誘導
体、ジベンズピレンキノン誘導体、ピラントロン誘導
体、ビオラントロン誘導体及びイソビオラントロン誘導
体等のアントラキノン系または多環キノン系顔料 (4)インジゴ誘導体及びチオインジゴ誘導体等のイン
ジゴイド系顔料 (5)金属フタロシアニン及び無金属フタロシアニン等
のフタロシアニン系顔料 (6)ジフェニルメタン系顔料、トリフェニルメタン顔
料、キサンテン顔料及びアクリジン顔料等のカルボニウ
ム系顔料 (7)アジン顔料、オキサジン顔料及びチアジン顔料等
のキノンイミン系顔料 (8)シアニン顔料及びアゾメチン顔料等のメチン系顔
料 (9)キノリン系顔料 (10)ニトロ系顔料 (11)ニトロン系顔料 (12)ベンゾキノン及びナフトキノン系顔料 (13)ナフタルイミド系顔料 (14)ビスベンズイミダゾール誘導体等のペリノン系顔
料 この中では感光体に高感度特性を付与しうるアゾ系顔
料、ペリレン系顔料、多環キノン系顔料、フタロシアニ
ン系顔料が好ましい。
(1) Azo pigments such as monoazo pigments, polyazo pigments, metal complex salt azo pigments, pyrazolone azo pigments, stilbene azo pigments and thiazole azo pigments (2) Perylene pigments such as perylene anhydride and perylene imide ( 3) Anthraquinone-based or polycyclic quinone-based pigments such as anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyrantrone derivatives, violanthrone derivatives and isobiolanthrone derivatives (4) Indigooid pigments such as indigo derivatives and thioindigo derivatives (4) 5) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine (6) Carbonium pigments such as diphenylmethane pigment, triphenylmethane pigment, xanthene pigment and acridine pigment (7) Azine pigment, oxazine face And quinone imine pigments such as thiazine pigments (8) Methine pigments such as cyanine pigments and azomethine pigments (9) Quinoline pigments (10) Nitro pigments (11) Nitron pigments (12) Benzoquinone and naphthoquinone pigments (13) Naphthalimide pigments (14) Perinone pigments such as bisbenzimidazole derivatives Among these, azo pigments, perylene pigments, polycyclic quinone pigments, and phthalocyanine pigments that can impart high sensitivity characteristics to the photoreceptor are preferable.

【0043】また前記CTLまたはCGLに含有される
CTMとしては、前記〔化1〕に示した一般式〔I〕ま
たは〔II〕で表される化合物が用いられ、それによって
高感度でしかも高耐久性で高信頼性の感光体をうること
ができる。
As the CTM contained in the CTL or CGL, the compound represented by the general formula [I] or [II] shown in the above [Chemical formula 1] is used, whereby high sensitivity and high durability are obtained. It is possible to obtain a photosensitive member having high reliability.

【0044】前記CGL及びCTLに含有されるバイン
ダ樹脂としては電子写真用の全ての樹脂が有用であり、
例えばポリエチレン、ポリプロピレン、アクリル樹脂、
メタクリル樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ビ
ニルブチラール樹脂、ビニルホルマール樹脂、エポキシ
樹脂、ポリウレタン樹脂、フェノール樹脂、ポリエステ
ル樹脂、アルキッド樹脂、ポリカーボネート樹脂、シリ
コーン樹脂、メラミン樹脂等の重付加型樹脂、重縮合型
樹脂、並びにこれらの樹脂の繰返し単位のうちの2つ以
上を含む共重合体樹脂、例えば塩化ビニル-酢酸ビニル
共重合体樹脂、塩化ビニル-酢酸ビニル-無水マレイン酸
共重合体樹脂等の絶縁性樹脂の他、ポリ-N-ビニルカル
バソール等の高分子有機半導体を挙げることができる。
As the binder resin contained in the CGL and CTL, all resins for electrophotography are useful,
For example, polyethylene, polypropylene, acrylic resin,
Methacrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl butyral resin, vinyl formal resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, etc. Condensation type resins, and copolymer resins containing two or more of repeating units of these resins, such as vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, etc. Other than the insulating resin, there may be mentioned polymer organic semiconductors such as poly-N-vinylcarbazole.

【0045】本発明に係る感光体の表面層を形成するC
TLとしては、層が均質、緻密、堅牢で通気性が小さい
等の特性が要請される。
C forming the surface layer of the photoreceptor according to the present invention
The TL is required to have properties such as a uniform layer, denseness, toughness, and low air permeability.

【0046】前記CTLを形成するのに適するバインダ
樹脂としては例えば熱硬化性エポキシ樹脂、メラミン樹
脂、フェノール樹脂、ウレタン樹脂、シリコーン樹脂、
アクリル樹脂、エステル樹脂等の熱硬化性樹脂がある。
As the binder resin suitable for forming the CTL, for example, thermosetting epoxy resin, melamine resin, phenol resin, urethane resin, silicone resin,
There are thermosetting resins such as acrylic resins and ester resins.

【0047】その他米国特許4,304,899号にも記載され
ているオゾン透過率を減少せしめうる下記の構成単位の
ポリマー化合物も好ましく用いられる。
Other polymer compounds described in US Pat. No. 4,304,899 having the following constitutional units capable of reducing the ozone transmittance are also preferably used.

【0048】[0048]

【化15】 [Chemical 15]

【0049】[0049]

【化16】 [Chemical 16]

【0050】前記本発明に係るCGL及びCTLに用い
られる分散媒あるいは溶剤としては、例えばn-ブチルア
ミン、ジエチルアミン、エチレンジアミン、イソプロパ
ノールアミン、モノエタノールアミン、トリエタノール
アミン、トリエチレンジアミン、N,N-ジメチルホルムア
ミド、アセトン、メチルエチルケトン、シクロヘキサノ
ン、ベンゼン、トルエン、キシレン、クロロホルム、1,
2-ジクロルエタン、ジクロルメタン、テトラヒドロフラ
ン、ジオキサン、メタノール、エタノール、イソプロパ
ノール、酢酸エチル、酢酸ブチル、ジメチルスルホキシ
ド、その他を用いることができる。
Examples of the dispersion medium or solvent used in the CGL and CTL according to the present invention include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, monoethanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide. , Acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,
2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide and the like can be used.

【0051】導電性支持体の材料としては、例えばアル
ミニウム、ニッケル、銅、亜鉛、パラジウム、銀、イン
ジウム、錫、白金、金、ステンレス鋼、真鍮等の金属シ
ートを用いることができる。
As the material of the conductive support, for example, a metal sheet of aluminum, nickel, copper, zinc, palladium, silver, indium, tin, platinum, gold, stainless steel, brass or the like can be used.

【0052】また、感光層内に感度の向上、残留電位な
いし反復使用時の疲労低減等を目的として、少なくとも
1種の電子受容性物質を含有せしめることができる。
Further, at least one electron-accepting substance can be contained in the photosensitive layer for the purpose of improving sensitivity, reducing residual potential or reducing fatigue during repeated use.

【0053】また更に表面改質剤としてシリコーンオイ
ル、弗素系界面活性剤を存在させてもよい。また耐久性
向上剤としてアンモニウム化合物が含有されていてもよ
い。
Further, a silicone oil or a fluorine-based surfactant may be present as a surface modifier. Further, an ammonium compound may be contained as a durability improver.

【0054】更に紫外線吸収剤を用いてもよい。好まし
い紫外線吸収剤としては、安息香酸、スチルベン化合物
等及びその誘導体、トリアゾール化合物、イミダゾール
化合物、トリアジン化合物、クマリン化合物、オキサジ
アゾール化合物、チアゾール化合物及びその誘導体等の
含窒素化合物類が用いられる。
Further, an ultraviolet absorber may be used. As preferable ultraviolet absorbers, nitrogen-containing compounds such as benzoic acid, stilbene compounds and their derivatives, triazole compounds, imidazole compounds, triazine compounds, coumarin compounds, oxadiazole compounds, thiazole compounds and their derivatives are used.

【0055】CTL,CGLに酸化防止剤を含有せしめ
ることができる。これにより放電発生するオゾンの影響
を抑制でき、繰返し使用時の残留電位上昇や帯電電位の
低下を防止できる。
An antioxidant can be contained in CTL and CGL. As a result, the influence of ozone generated by discharge can be suppressed, and it is possible to prevent an increase in residual potential and a decrease in charging potential during repeated use.

【0056】酸化防止剤としては、ヒンダードフェノー
ル、ヒンダードアミン、パラフェニレンジアミン、アリ
ールアルカン、ハイドロキノン、スピロクロマン、スピ
ロインダノン及びそれらの誘導体、有機硫黄化合物、有
機燐化合物等が挙げられる。これらの具体的化合物とし
ては、特開昭63-44667号、同63-50848号、同63-14153
号、同63-50849号、同63-18355号、同63-58455号、同63
-71857号、同63-71856号及び同63-146046号に記載があ
る。
Examples of the antioxidants include hindered phenols, hindered amines, paraphenylenediamines, aryl alkanes, hydroquinones, spirochromans, spiroindanones and their derivatives, organic sulfur compounds and organic phosphorus compounds. Specific examples of these compounds include JP-A Nos. 63-44667, 63-50848, and 63-14153.
63, 50849, 63-18355, 63-58455, 63
-71857, 63-71856 and 63-146046.

【0057】次に本発明に係る導電性支持体上にCGL
及びCTLをこの順に積層して成る感光体の前記CTL
の単位膜厚当りの酸素ガス透過係数の具体的測定法につ
いて以下に説明する。
Next, CGL is formed on the conductive support according to the present invention.
And CTL of the photoconductor formed by laminating CTL in this order.
A specific method of measuring the oxygen gas permeation coefficient per unit film thickness of is described below.

【0058】図2(a)は、具体的な測定装置による測
定系統を示す概略図である。
FIG. 2A is a schematic diagram showing a measuring system by a specific measuring device.

【0059】図において、測定試料10を保持するセル11
は恒温槽18内に保持され、該セル11の高圧側に気体(酸
素ガス)透過係数測定用酸素ガスを導入する。時間経過
と共に前記高圧側の酸素ガスが試料10を透過して低圧側
に移動し、低圧側の圧力が変化する。
In the figure, a cell 11 holding a measurement sample 10 is shown.
Is held in a constant temperature bath 18, and oxygen gas for gas (oxygen gas) permeation coefficient measurement is introduced into the high pressure side of the cell 11. The oxygen gas on the high pressure side permeates the sample 10 and moves to the low pressure side with the lapse of time, and the pressure on the low pressure side changes.

【0060】前記低圧側の圧力変化を微差圧トランジュ
ーサ12で読取り、電気的信号として出力し、これは記録
計17で増幅記録される。なお図中13は低圧側用拡散ポン
プ、14はトラップ、15は真空計、16は感度変更用予備ボ
リュームである。
The pressure change on the low pressure side is read by the slight differential pressure transducer 12 and output as an electric signal, which is amplified and recorded by the recorder 17. In the figure, 13 is a low-pressure side diffusion pump, 14 is a trap, 15 is a vacuum gauge, and 16 is a spare volume for sensitivity change.

【0061】同図(b)は前記増幅記録された酸素ガス
透過曲線を示しており、この曲線から該曲線の直線部の
勾配ΔPb/Δtを求め、これを下記式に代入すること
により測定試料10の単位膜厚当りの酸素ガス透過係数P
/lを求めることができる。
FIG. 11B shows the oxygen gas permeation curve recorded by amplification, and the gradient ΔP b / Δt of the straight line portion of the curve is determined from this curve and measured by substituting it into the following equation. Oxygen gas permeation coefficient P per unit film thickness of sample 10
/ L can be obtained.

【0062】[0062]

【数1】 [Equation 1]

【0063】 P :気体透過係数 (cc/cm2・S・cmHg)(s:秒) V :低圧側容積 (cc) A :透過面積 cm2 l :測定試料の膜厚 cm Po :標準圧力 〔1atm=76cmHg〕 Pa :高圧側の圧力 〔cmHg〕 Pb :低圧側の圧力 〔cmHg〕 To :標準温度 〔273°K〕 T :測定温度 〔K〕 ΔPb/Δt:定常状態における低圧側圧力の増加速度
即ち透過曲線の直線部分の勾配 〔cmHg/s〕 上記した「酸素の気体透過係数」は、バインダ、物質の
種類、化学式、重合度によって変ることは勿論だが、そ
れだけではなく、CTLの塗膜を形成する際の塗布溶
媒、塗布方法、乾燥の度合、塗布液中のCTM及びバイ
ンダ物質濃度等の因子によっても変動するものである。
即ちCTL膜中のバインダとCTMの相溶性が良好であ
ることは勿論、その他の添加剤との相溶性もよく、均質
な膜である事は「酸素の気体透過係数」を低くする為に
は必要である。
P: Gas permeation coefficient (cc / cm 2 · S · cmHg) (s: second) V: Low-pressure side volume (cc) A: Permeation area cm 2 l: Film thickness of measurement sample cm Po : Standard pressure [1atm = 76cmHg] P a: pressure [cmHg] P b of the high pressure side: low pressure side of the pressure [cmHg] T o: standard temperature [273 ° K] T: measurement temperature [K] [Delta] P b / Delta] t: at steady state The rate of increase of the pressure on the low pressure side, that is, the slope of the linear part of the permeation curve [cmHg / s] The above "gas permeability coefficient of oxygen" may vary depending on the binder, the type of substance, the chemical formula, and the degree of polymerization, but not only that. , The coating solvent for forming the CTL coating film, the coating method, the degree of drying, the CTM in the coating liquid, the concentration of the binder substance, and other factors.
That is, the compatibility of the binder and CTM in the CTL film is good, as well as the compatibility with other additives, and the fact that the film is homogeneous means that the "gas permeability coefficient of oxygen" can be lowered. is necessary.

【0064】本発明に係る感光体では、感光層の表面層
としてのCTLの酸素ガス透過係数を前記のように特定
範囲に限定した点に特徴があり、それによって酸素ガ
ス、特にオゾンガス等のCTLへの侵入が抑止され、C
TM等の劣化が低く抑えられる。
The photoconductor according to the present invention is characterized in that the oxygen gas permeation coefficient of CTL as the surface layer of the photosensitive layer is limited to a specific range as described above, whereby the CTL of oxygen gas, particularly ozone gas, etc. Is prevented from entering the
Deterioration of TM etc. can be suppressed low.

【0065】次に本発明の画像形成装置の構成について
は特に限定はなく、一般的な下記構造の画像形成装置に
より装置内のオゾン濃度を測定する測定法を説明する。
The structure of the image forming apparatus of the present invention is not particularly limited, and a measuring method for measuring the ozone concentration in the apparatus by a general image forming apparatus having the following structure will be described.

【0066】図3は前記画像形成装置の一般的な構成を
示すもので、21は原稿載置台、22は原稿、23は原稿押え
カバーで、像露光用光学系は、投光ユニット24、露光ラ
ンプ25、ミラーユニット26、反射ミラー27、結像レンズ
28、反射ミラー29等から成り、前記光学系を介して予め
帯電ローラ31によって一様帯電された感光体20上に像露
光されて静電潜像が形成される。この静電潜像は現像装
置32のスリーブ33により搬送された現像剤により現像さ
れてトナー像が形成される。
FIG. 3 shows the general structure of the image forming apparatus. Reference numeral 21 is a document mounting table, 22 is a document, 23 is a document pressing cover, and the image exposure optical system is a light projecting unit 24 and an exposure unit. Lamp 25, mirror unit 26, reflection mirror 27, imaging lens
An electrostatic latent image is formed on the photoconductor 20 which is composed of a reflecting mirror 29, a reflecting mirror 29 and the like, and which has been uniformly charged by the charging roller 31 in advance through the optical system. This electrostatic latent image is developed by the developer carried by the sleeve 33 of the developing device 32 to form a toner image.

【0067】該トナー像は、給紙カセット35の給紙ロー
ラ36により搬送された複写紙37に転写ローラ38によって
転写され、感光体20から分離された後搬送ベルト40によ
り定着装置41に送られ、加熱ローラ42と押圧ローラ43の
圧接下に定着される。転写後の感光体20は除電ランプ34
により除電された後、クリーニング装置47のブレード47
Aにより清掃され、次の像形成に設けられる。
The toner image is transferred by the transfer roller 38 onto the copy paper 37 carried by the paper feed roller 36 of the paper feed cassette 35, separated from the photoconductor 20 and then sent to the fixing device 41 by the carrying belt 40. It is fixed under pressure between the heating roller 42 and the pressing roller 43. After the transfer, the photoconductor 20 has a static elimination lamp 34.
After the charge is removed by the blade 47 of the cleaning device 47
It is cleaned by A and is prepared for the next image formation.

【0068】前記帯電ローラ31及び転写ローラ38には、
電源49からDC及び必要によりACバイアス電圧が印加
され、感光体ドラム20への帯電及びトナー像の転写紙27
への転写が行われる。前記バイアス電圧としては、通常
500〜1000VのDCバイアスが印加され、必要により100
Hz〜10KHz,Vp-p200〜3500VのACバイアスが重畳さ
れてもよい。
The charging roller 31 and the transfer roller 38 are
DC and, if necessary, AC bias voltage are applied from the power source 49 to charge the photosensitive drum 20 and transfer the toner image to the transfer paper 27.
Transfer to. The bias voltage is usually
DC bias of 500-1000V is applied, and if necessary 100
An AC bias of Hz to 10 KHz and V pp 200 to 3500 V may be superimposed.

【0069】前記バイアス電圧が印加された帯電ローラ
31(及び転写ローラ38)は、感光体の摩粍、損傷を防止
するため、図4(a)のローラ圧接・離間手段により、
不要時は感光体ドラム20から離間されることが好まし
い。図4(a)の50はローラ31を軸51を中心に回動可能
に支持するレバーであり、バネ52はローラ31を上方に付
勢していて、不要時には該ローラ31を感光体ドラム20か
ら離間させ、帯電(または転写)時には、偏心カム53の
回動により、前記バネ52のバネ圧に抗して前記ローラ31
(または38)を感光体ドラム20に圧接させ、感光体ドラ
ム20との従動回転(または強制回転)下に帯電(または
転写)が行われる。
Charging roller to which the bias voltage is applied
In order to prevent abrasion and damage of the photoconductor, the roller 31 (and the transfer roller 38) is provided with the roller pressure contact / separation means of FIG.
When unnecessary, it is preferably separated from the photoconductor drum 20. Reference numeral 50 in FIG. 4A is a lever for rotatably supporting the roller 31 about a shaft 51, and a spring 52 urges the roller 31 upward. At the time of charging (or transfer), the roller 31 is rotated against the spring pressure of the spring 52 by the rotation of the eccentric cam 53.
(Or 38) is brought into pressure contact with the photosensitive drum 20, and charging (or transfer) is performed under the driven rotation (or forced rotation) with the photosensitive drum 20.

【0070】前記ローラ31(または38)の感光体ドラム
20への圧接は10〜100g/cmとされ、ローラ31(または3
8)の回転は感光体ドラム20の周速の1〜8倍とされ
る。
Photosensitive drum of the roller 31 (or 38)
The pressure contact with 20 is 10 to 100 g / cm, and roller 31 (or 3
The rotation of 8) is 1 to 8 times the peripheral speed of the photosensitive drum 20.

【0071】また、ローラ31(または38)の断面構成は
図4(b)に示すように芯金55の外周に導電性クロルプ
レンゴム、ウレタンゴム、シリコーンゴム等のゴム層ま
たはそれらの発泡層から成り、好ましくは最外層に0.01
〜1μmの離型性弗素樹脂またはシリコーン樹脂層から
成る保護層を設けて構成される。
As shown in FIG. 4 (b), the roller 31 (or 38) has a cross-sectional structure in which a rubber layer of conductive chloroprene rubber, urethane rubber, silicone rubber, or the like, or a foamed layer thereof is formed on the outer periphery of the core 55. Consists of 0.01, preferably 0.01 in the outermost layer
It is constituted by providing a protective layer composed of a releasable fluororesin or silicone resin layer having a thickness of 1 μm.

【0072】前記画像形成装置内のオゾンガス濃度を測
定するには、エバラ実業(株)製オゾンモニタEG-200
1Rが組込まれた東洋精機製作所(株)製オゾンテスタ
が用いられる。
To measure the ozone gas concentration in the image forming apparatus, an ozone monitor EG-200 manufactured by Ebara Jitsugyo Co., Ltd. is used.
An ozone tester manufactured by Toyo Seiki Seisakusho Co., Ltd. in which 1R is incorporated is used.

【0073】図3の画像形成装置を例として説明すれ
ば、試料ガス採取用テフロンチューブの端(試料ガス採
取口)を前記装置の符号Pで指定した位置に設置し、前
記チューブの他端を前記オゾンモニタの試料ガス導入口
に嵌装し、前記画像形成装置からのオゾンガス濃度をモ
ニタのデジタルデータ表示がppm単位で読取る。
To describe the image forming apparatus of FIG. 3 as an example, the end of the Teflon tube for sample gas sampling (sample gas sampling port) is installed at the position designated by the symbol P of the apparatus, and the other end of the tube is set. It is fitted into the sample gas inlet of the ozone monitor, and the ozone gas concentration from the image forming apparatus is read by the digital data display of the monitor in ppm.

【0074】なお、前記画像形成装置内の測定位置Pは
クリーニング装置47と帯電ローラ31との間で、かつ感光
体ドラム20から5m/mの間隙をおいて配置される。
The measurement position P in the image forming apparatus is arranged between the cleaning device 47 and the charging roller 31 and at a distance of 5 m / m from the photosensitive drum 20.

【0075】本発明では、前記オゾンテスタに組込まれ
たオゾンモニタにより、前記測定位置Pで測定したとき
のオゾンガス濃度が0.5ppm以下であることが必須の要件
とされ、0.5ppmを越えると高感度感光体、特に前記特定
構造のCTMを用いた感光体の繰返し特性が悪く、帯電
電位、感度、残留電位等の特性の劣化が顕著になる。以
下本発明の実施例により具体的に説明するが本発明の実
施の態様がこれにより限定されるものではない。
In the present invention, the ozone monitor incorporated in the ozone tester is required to have an ozone gas concentration of 0.5 ppm or less when measured at the measuring position P. If it exceeds 0.5 ppm, high sensitivity photosensitivity is obtained. The repetitive characteristics of the body, especially the photoreceptor using the CTM having the above-mentioned specific structure, are poor, and the characteristics such as charging potential, sensitivity, residual potential, etc. are significantly deteriorated. Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited thereto.

【0076】[0076]

【実施例】【Example】

〈感光体及び特性測定試料の作成〉 (感光体の作成)80mmφのアルミニウム製円筒状ドラム
(シリンダ)上に、塩化ビニル-酢酸ビニル-無水マレイ
ン酸共重合体「エスレックMF-10」(積水化学工業社
製)より成る厚さ約0.1μmの中間層を設けた。次に、下
記〔化17〕に示す構造式を有するビスアゾ顔料4gをボ
ールミルで24時間粉砕し、これにビスフェノールA型ポ
リカーボネート「パンライトL-1250」(帝人化成社
製)(以下BPAと称する)2gを1,2-ジクロルエタン1
30mlに溶解した溶液を加えて、更に24時間分散し、得ら
れた分散液を前記中間層上に浸漬塗布し、十分乾燥して
厚さ約0.5μmのCGLを形成した。
<Preparation of photoconductor and characteristic measurement sample> (Preparation of photoconductor) A vinyl chloride-vinyl acetate-maleic anhydride copolymer "ESREC MF-10" (Sekisui Chemical Co., Ltd.) was placed on an 80 mmφ aluminum cylindrical drum. An intermediate layer having a thickness of about 0.1 μm, which is made by Kogyo Co., Ltd. Next, 4 g of the bisazo pigment having the structural formula shown in the following [Chemical Formula 17] was crushed with a ball mill for 24 hours, and bisphenol A type polycarbonate "Panlite L-1250" (manufactured by Teijin Chemicals Ltd.) (hereinafter referred to as BPA). 2 g of 1,2-dichloroethane 1
A solution dissolved in 30 ml was added and dispersed for another 24 hours. The obtained dispersion was dip-coated on the intermediate layer and sufficiently dried to form a CGL having a thickness of about 0.5 μm.

【0077】次にCTMとして、例示化合物II−(1);
10gとバインダ樹脂として例示化合物III−(6)を構成単
位とする粘度平均分子量20000のポリカーボネート(ジ
メチルBPZと仮称する)10gとを1,2-ジクロルエタン1
00mlに溶解して得た溶液を上記CGL上に浸漬塗布し、
温度80℃にて1時間乾燥して厚さ20μmのCTLを形成
して感光体1を得た。
Next, as CTM, exemplified compound II- (1);
1,2-dichloroethane 1 of 10 g and 10 g of a polycarbonate having a viscosity average molecular weight of 20000 (tentatively referred to as dimethyl BPZ) containing Exemplified Compound III- (6) as a binder resin
The solution obtained by dissolving in 00 ml is dip-coated on the CGL,
By drying at a temperature of 80 ° C. for 1 hour, a CTL having a thickness of 20 μm was formed to obtain a photoconductor 1.

【0078】[0078]

【化17】 [Chemical 17]

【0079】なお前記浸漬塗布は図5(a)及び同図
(b)の塗布装置を用いて塗布加工された。前記図5に
おいて、塗布液112を収容した塗布容器113に対し、支持
棒119を貫通せしめることによって保持されたアルミ製
円筒111が上下動可能に配されている。図5(a)は、
円筒111を下降せしめて塗布液112内に充分に浸漬した状
態を示す。容器113上には、溶媒蒸気濃度分布を調節す
るための貫通孔115を側部に設けた円筒状カバー部材114
が容器113とほぼ同径に連設されていて、その内側は乾
燥領域124となっている。
The dip coating was applied using the coating apparatus shown in FIGS. 5 (a) and 5 (b). In FIG. 5, an aluminum cylinder 111 held by penetrating a support rod 119 is arranged in a coating container 113 containing a coating liquid 112 so as to be vertically movable. Figure 5 (a) shows
The state where the cylinder 111 is lowered and sufficiently immersed in the coating liquid 112 is shown. On the container 113, a cylindrical cover member 114 having through holes 115 on its side for adjusting the solvent vapor concentration distribution is provided.
Are continuously connected to the container 113 with substantially the same diameter, and the inside thereof is a drying region 124.

【0080】従って、図5(b)に示す如く、図5
(a)の浸漬状態(図5(b)では一点鎖線で示す)か
ら、蒸気支持棒119を固定したアーム118を上昇させるこ
とにより同図(b)の実線、更には二点鎖線で示すよう
に円筒111を塗布液112から引上げ、乾燥領域124内を所
定の速度で通過させるように構成している。円筒111を
乾燥領域124(即ちカバー部材114)の外部に引上げた状
態から、新たな円筒を下降させ、上記した動作を繰返せ
ば円筒外面の塗布液112への浸漬、塗布液112の塗布・乾
燥を再び行うことができる。
Therefore, as shown in FIG.
From the immersion state of (a) (shown by the one-dot chain line in FIG. 5 (b)), the arm 118 to which the steam support rod 119 is fixed is raised so that the solid line of FIG. In addition, the cylinder 111 is pulled up from the coating liquid 112 and passed through the drying area 124 at a predetermined speed. From the state where the cylinder 111 is pulled up to the outside of the dry area 124 (that is, the cover member 114), a new cylinder is lowered, and if the above-described operation is repeated, the cylinder outer surface is dipped in the coating liquid 112, and the coating liquid 112 is applied. The drying can be carried out again.

【0081】なお、円筒111の上下開口に蓋125,126を
被せ、ナット120で締め付けることにより、円筒111内に
塗布液112が侵入しないようにしておくのが好ましい
(但し、上部側の蓋125は円筒111の浸漬深さによっては
必ずしも設けることを要しない)。
It is preferable that the upper and lower openings of the cylinder 111 are covered with the lids 125 and 126 and the nut 120 is tightened to prevent the coating liquid 112 from entering the cylinder 111 (however, the lid 125 on the upper side). Is not necessarily required depending on the immersion depth of the cylinder 111).

【0082】一方、上記アーム118の上下動機構は次の
如くに構成されている。即ち、基板122上に支柱121a,
121bが鉛直方向に固定され、それらの上端は上基板123
に固定されている。この上基板123には垂直下方へ延び
る送りねじ棒116が軸支されている。この送りねじ棒116
の下端は支柱121a,121bに固定された固定板127の中
央部を貫通して、固定板127の下面に固定されたモータ1
17の回転軸と一体になっている。上記アーム118には上
記送りねじ棒116に対応した雌ねじ128が切られていて、
この雌ねじに螺合させながら送りねじ棒116をアーム118
に貫通させ、これによってアーム118が送りねじ棒116に
支持されつつ、モータ117による送りねじ棒116の回転に
伴って上下動せしめることになる。
On the other hand, the vertical moving mechanism of the arm 118 is constructed as follows. That is, the columns 121a,
121b are fixed vertically, and their upper ends are upper substrate 123.
It is fixed to. A feed screw rod 116 extending vertically downward is pivotally supported on the upper substrate 123. This lead screw rod 116
Of the motor 1 fixed to the lower surface of the fixing plate 127 through the central portion of the fixing plate 127 fixed to the columns 121a and 121b.
It is integrated with 17 rotating shafts. A female screw 128 corresponding to the feed screw rod 116 is cut on the arm 118,
While screwing this female screw, the feed screw rod 116 is attached to the arm 118.
Thus, the arm 118 is supported by the feed screw rod 116 and can be moved up and down as the feed screw rod 116 is rotated by the motor 117.

【0083】次にCTLのバインダ樹脂として感光体1
の(ジメチルBPZ10g)に代えて(ジメチルBPZ7.5
gとBPA2.5g)とした他は感光体1と同様にして感光
体2を得た。また感光体1のCTLのバインダ樹脂であ
る(ジメチルBPZ10g)及びCTMである例示化合物I
I−(1)に代えてバインダ樹脂を(ジメチルBPZ5.0g
とBPA5.0g)、(ジメチルBPZ2.5gとBPA7.5g)
及び(BPA10g)にそれぞれ変化し、かつCTMとし
て例示化合物I−(2)とした他は感光体1と同様にして
感光体3、感光体4及び感光体5を得た。
Next, the photosensitive member 1 was used as the binder resin for CTL.
Instead of (dimethyl BPZ10g), (dimethyl BPZ7.5
g and BPA 2.5 g), and photoconductor 2 was obtained in the same manner as photoconductor 1. Exemplified Compound I which is the binder resin of CTL of the photoconductor 1 (dimethyl BPZ 10 g) and CTM
Instead of I- (1), a binder resin (dimethyl BPZ 5.0 g
And BPA 5.0g), (dimethyl BPZ 2.5g and BPA 7.5g)
And (BPA10 g) respectively, and photoconductor 3, photoconductor 4 and photoconductor 5 were obtained in the same manner as photoconductor 1 except that exemplified compound I- (2) was used as CTM.

【0084】(静電特性測定試料(E)の作成)前記感
光体1〜5のアルミ円筒ドラムに代えてアルミ箱をラミ
ネートしたPETベースを用いた他は感光体1と同様に
して前記感光体1〜5に対応する感光体E1〜E5を得
た。
(Preparation of Electrostatic Property Measurement Sample (E)) The photoconductor was the same as the photoconductor 1 except that a PET base laminated with an aluminum box was used instead of the aluminum cylindrical drums of the photoconductors 1 to 5. Photoconductors E1 to E5 corresponding to Nos. 1 to 5 were obtained.

【0085】次にこれらの5種類の感光板のそれぞれか
ら約40×40mm角の測定試料4枚ずつ採取し、感光体E−
1からE−1−1〜E−1−4、感光板E−2からE−
2−1〜E−2−4、感光板E−3からE−3−1〜E
−3−4、感光板E−4からE−4−1〜E−4−4及
び感光板E−5からE−5−1〜E−5−4の各測定試
料を得た。これらをグループ別に区分し、まず第1グル
ープ(E−1−1〜E−5−1)の試料を前記オゾンモ
ニタEG-2001Rが組込まれたエバラのオゾンテスタ試
験槽に挿入し、該試験槽に前記オゾンテスタのオゾン発
生機から0.1ppmのオゾンガスを導入し、25℃で30日間に
亘り保存して第1グループのエレクトロメータ測定試料
を得た。
Next, four measurement samples of about 40 × 40 mm square were taken from each of these five types of photosensitive plates, and the photosensitive member E-
1 to E-1-1 to E-1-4, photosensitive plates E-2 to E-
2-1 to E-2-4, photosensitive plate E-3 to E-3-1 to E-
-3-4, photosensitive plates E-4 to E-4-1 to E-4-4 and photosensitive plates E-5 to E-5-1 to E-5-4 were obtained. These are divided into groups, and first, the samples of the first group (E-1-1 to E-5-1) are inserted into the Ebara ozone tester test tank in which the ozone monitor EG-2001R is incorporated, and then the test tanks are put into the test tank. Ozone gas of 0.1 ppm was introduced from the ozone generator of the ozone tester and stored at 25 ° C. for 30 days to obtain a first group of electrometer measurement samples.

【0086】なお前記オゾンガスの温度はモニタ表示板
にデジタルデータとして表示される外、30日間のオゾン
濃度の変動がレコーダに自動記録される。
The temperature of the ozone gas is displayed as digital data on the monitor display plate, and the fluctuation of the ozone concentration for 30 days is automatically recorded in the recorder.

【0087】次いで前記第2グループ(E−1−2〜E
−5−2)、第3グループ(E−1−3〜E−5−3)
及び第4グループ(E−1−4〜E−5−4)をそれぞ
れオゾン濃度0.5ppm,0.6ppm及び1.0ppmとした他は第1
グループの場合と同様にして第2、第3及び第4グルー
プのエレクトロメータ測定試料を得た。
Next, the second group (E-1-2 to E)
-5-2), the third group (E-1-3 to E-5-3)
And the fourth group (E-1-4 to E-5-4) has ozone concentrations of 0.5 ppm, 0.6 ppm and 1.0 ppm, respectively.
Electrometer measurement samples of the second, third and fourth groups were obtained in the same manner as in the group.

【0088】(静電特性の測定)これら4グループ16枚
のエレクトロメータ測定用試料は順次エレクトロメータ
「EPA-8100」(川口電機製作所製)に装着して静電
特性が測定された。
(Measurement of Electrostatic Characteristic) These four groups of 16 electrometer measurement samples were sequentially mounted on an electrometer "EPA-8100" (manufactured by Kawaguchi Electric Co., Ltd.) to measure electrostatic characteristics.

【0089】即ち、試料表面を帯電圧−6.0KVで5秒間
帯電せしめた時の表面電位VA、次いでタングステンラ
ンプの光を感光体表面における照度が30luxになるよう
にして照射し、表面電位VAを半分に減衰させるのに要
する露光量(半減露光量)E1/2(lux・sec)、並びに30
lux・secの露光量で露光した後の表面電位(残留電位)
VRをそれぞれ求め、得られた値を表1に示した。
That is, the surface potential VA when the surface of the sample was charged with a charging voltage of -6.0 KV for 5 seconds, and then the light of a tungsten lamp was irradiated so that the illuminance on the surface of the photosensitive member was 30 lux, and the surface potential VA was changed. Exposure amount required to attenuate to half (half exposure amount) E1 / 2 (lux · sec), and 30
Surface potential (residual potential) after exposure with an exposure of lux · sec
The respective VRs were determined and the obtained values are shown in Table 1.

【0090】[0090]

【表1】 [Table 1]

【0091】(酸素ガス透過係数測定試料(T)の作
成)感光体1〜5のCTLの各塗布液を、径80mmのアル
ミ製円筒上にPETベースを巻き付けた上に前記図5の
浸漬塗布装置を用いてそれぞれ塗布加工も、これを90℃
で24時間乾燥し、冷却後、PETベースからCTLを剥
離して感光体1〜5に対応するCTLから成る20μm厚
の酸素ガス透過係数測定試料T−1〜T−5を得た。
(Preparation of Oxygen Gas Permeability Coefficient Measurement Sample (T)) Each coating solution of CTL of the photoconductors 1 to 5 was wound around a PET base on an aluminum cylinder having a diameter of 80 mm, and was applied by dip coating as shown in FIG. The coating process using the equipment is 90 ℃
After drying for 24 hours and cooling, the CTL was peeled off from the PET base to obtain oxygen gas permeation coefficient measurement samples T-1 to T-5 having a thickness of 20 μm and composed of CTLs corresponding to the photoconductors 1 to 5.

【0092】(酸素ガス透過係数の測定)前記各測定試
料(T1〜T5)を順次図2のガス透過係数測定装置のセ
ル11に設定し、恒温槽18の温度を35℃とし、酸素ガスを
用いて測定を行った。
(Measurement of Oxygen Gas Permeability Coefficient) The respective measurement samples (T 1 to T 5 ) were sequentially set in the cell 11 of the gas permeability coefficient measuring device of FIG. The measurement was performed using gas.

【0093】測定方法は前記したように、各測定試料に
一定の酸素ガス厚Pa(高圧側)を加えると、時間tの
経過と共に高圧側の酸素ガスが前記試料を透過して低圧
側(ガス圧Pb)に移行し、低圧側のガス圧Pbが変化す
る。
As described above, when a constant oxygen gas thickness P a (high pressure side) is applied to each measurement sample as described above, the oxygen gas on the high pressure side permeates the sample with the lapse of time t and the low pressure side ( goes to the gas pressure P b), a change in the gas pressure P b of the low-pressure side.

【0094】前記経過時間tに対する低圧側の酸素ガス
圧Pbの変化をプロットして図2(b)の如き透過曲線
を作成し、その曲線の直線部分の勾配ΔPb/Δtを求
め、これを前記気体透過係数の式に代入して単位膜厚当
りの酸素ガス透過係数を算出し、その結果を表2に示し
た。
The change of the oxygen gas pressure P b on the low pressure side with respect to the elapsed time t is plotted to create a permeation curve as shown in FIG. 2 (b), and the gradient ΔP b / Δt of the linear portion of the curve is determined. Was substituted into the above equation of the gas permeability coefficient to calculate the oxygen gas permeability coefficient per unit film thickness, and the results are shown in Table 2.

【0095】[0095]

【表2】 [Table 2]

【0096】〈実写テスト〉 実施例1 コニカ社製U-Bix 3035に感光体1を装着し、帯電器及び
転写器として前記図3及び4で説明した帯電ローラ及び
転写ローラを組込んだ改造機を用い、20℃,RH60%の
雰囲気下で20万回に亘り繰返し像形成を行ない、初期と
20万回目の画質を評価し、その結果を表3に示した。
<Actual Shooting Test> Example 1 A modified machine in which the photoconductor 1 is mounted on the U-Bix 3035 manufactured by Konica and the charging roller and the transfer roller described in FIGS. 3 and 4 are incorporated as the charging device and the transfer device. Image formation was repeated 200,000 times in an atmosphere of 20 ° C and 60% RH.
The image quality at the 200,000th time was evaluated, and the results are shown in Table 3.

【0097】なお、画質評価の際のかぶり濃度及びDmax
(Maximum Density)測定用濃度計はMacbeth RD918を用
いた。
The fog density and Dmax at the time of image quality evaluation
(Maximum Density) Macbeth RD918 was used as a densitometer for measurement.

【0098】実施例2及び3 実施例1の感光体1に代えて感光体2及び3を用いた他
は実施例1と同様にして像形成を行ない、画質を評価す
ると共にオゾン濃度を測定し、その結果を表3に示し
た。
Examples 2 and 3 Image formation was performed in the same manner as in Example 1 except that the photoconductors 2 and 3 were used instead of the photoconductor 1 of Example 1, the image quality was evaluated, and the ozone concentration was measured. The results are shown in Table 3.

【0099】比較例(1)及び(2) 実施例1の感光体1に代えて感光体4及び5を用いた他
は実施例と同様にして像形成を行ない、画質を評価する
と共にオゾン濃度を測定し、その結果を表3に示した。
Comparative Examples (1) and (2) Image formation was carried out in the same manner as in Example 1 except that the photoconductors 4 and 5 were used in place of the photoconductor 1 of Example 1, the image quality was evaluated, and the ozone concentration was determined. Was measured and the results are shown in Table 3.

【0100】比較例(3) 実施例1の帯電ローラ及び転写ローラに代えてコロナ放
電器を用いた他は実施例1と同様にして像形成を行な
い、画質を評価しかつオゾン濃度を測定し、その結果を
表3に示した。
Comparative Example (3) Image formation was performed in the same manner as in Example 1 except that a corona discharger was used instead of the charging roller and the transfer roller in Example 1, the image quality was evaluated, and the ozone concentration was measured. The results are shown in Table 3.

【0101】[0101]

【表3】 [Table 3]

【0102】以上の表1,表2及び表3から明らかなよ
うに、画像形成装置に、酸素ガス等のガスを透過しにく
いCTLを有する感光体が装着され、且つ前記装置内の
オゾン濃度が0.5ppm以下とされていることから、前記装
置を用いて像形成を行った場合、像形成の初期から長期
に亘り画像劣化を生ぜず、高画質が安定して得られるこ
とがわかる。
As is clear from Table 1, Table 2 and Table 3 described above, the image forming apparatus is equipped with the photoconductor having the CTL which hardly permeates gas such as oxygen gas, and the ozone concentration in the apparatus is Since the content is 0.5 ppm or less, it is understood that when image formation is performed using the above apparatus, high image quality is stably obtained without causing image deterioration for a long period from the initial stage of image formation.

【0103】[0103]

【発明の効果】以上の説明から明らかなように、本発明
の画像形成装置によれば、電子写真性能に優れた電荷輸
送物質の選択の自由度が大で、電子写真性が優れ、特に
高感度特性を有する感光体を用いて長期の繰返し像形成
の過程で疲労劣化が少なく良質の画像が安定して提供で
きる等の効果が奏される。
As is apparent from the above description, according to the image forming apparatus of the present invention, the degree of freedom in selection of the charge transporting material having excellent electrophotographic performance is high, the electrophotographic property is excellent, and the electrophotographic property is particularly high. With the use of a photoreceptor having sensitivity characteristics, fatigue deterioration is less likely to occur in the course of repeated image formation for a long period of time, and a high-quality image can be stably provided.

【図面の簡単な説明】[Brief description of drawings]

【図1】感光体の層構成を示す断面図。FIG. 1 is a cross-sectional view showing a layer structure of a photoconductor.

【図2】(a)はガス透過係数測定装置の構成図及び
(b)は経過時間tと低圧側圧力Pbとの関係図。
FIG. 2A is a configuration diagram of a gas permeation coefficient measuring device, and FIG. 2B is a relationship diagram between an elapsed time t and a low pressure side pressure P b .

【図3】本発明に用いられる画像形成装置。FIG. 3 is an image forming apparatus used in the present invention.

【図4】(a)は圧接,離間手段を有する帯電ローラ,
転写ローラの構成図、(b)はローラの断面図。
FIG. 4A is a charging roller having a pressure contact / separation unit,
The transfer roller configuration diagram, (b) is a sectional view of the roller.

【図5】(a),(b)は浸漬塗布装置の断面図。5A and 5B are cross-sectional views of the dip coating device.

【符号の説明】[Explanation of symbols]

1 導電性支持体 2 中間層 3 CGL 4 CTL 11 セル 18 恒温槽 20 像形成体(感光体) 31 帯電ローラ 38 転写ローラ P 測定点 47 クリーニング装置 48 バイアス 53 カム 1 conductive support 2 intermediate layer 3 CGL 4 CTL 11 cell 18 thermostat 20 image forming body (photoconductor) 31 charging roller 38 transfer roller P measuring point 47 cleaning device 48 bias 53 cam

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 少くとも電子写真感光体と、該感光体の
外周に帯電、露光、現像、転写及びクリーニングの各手
段を有する画像形成装置において、該装置内のオゾン濃
度が0.5ppm以下であり、且つ前記感光体の最上層が電荷
輸送物質として下記一般式〔I〕または〔II〕で示され
る化合物を含有する電荷輸送層で構成され、該電荷輸送
層の単位膜厚当りの酸素ガス透過係数が1.0×10-7(cc/
cm2・S・cmHg)以下であることを特徴とする画像形成装
置。 【化1】 〔前記一般式〔I〕において、Ar1,Ar2は同じでも異
なってもよく、各々置換,非置換のフェニル基を表す。
Ar3は置換,非置換のアリーレン基を表す。Ar4は置
換,非置換のアリール基、フリル基、チエニル基を表
す。更に、前記一般式〔II〕において、Ar5,Ar6及び
Ar7は置換,非置換のアリール基、芳香族置換アルキル
基及び置換、非置換の複素環を表し、R1及びR2は水素
原子、置換,非置換のアルキル基、置換,非置換のアリ
ール基を表し、Ar8は置換,非置換のアリーレン基を表
す。〕
1. An image forming apparatus having at least an electrophotographic photosensitive member and means for charging, exposing, developing, transferring and cleaning the outer periphery of the photosensitive member, wherein the ozone concentration in the apparatus is 0.5 ppm or less. And the uppermost layer of the photoreceptor is composed of a charge transport layer containing a compound represented by the following general formula [I] or [II] as a charge transport substance, and oxygen gas permeation per unit film thickness of the charge transport layer Coefficient is 1.0 × 10 -7 (cc /
cm 2 · S · cmHg) or less, the image forming apparatus. [Chemical 1] [In the above general formula [I], Ar 1 and Ar 2 may be the same or different and each represents a substituted or unsubstituted phenyl group.
Ar 3 represents a substituted or unsubstituted arylene group. Ar 4 represents a substituted or unsubstituted aryl group, furyl group or thienyl group. Further, in the above general formula [II], Ar 5 , Ar 6 and Ar 7 represent a substituted or unsubstituted aryl group, an aromatic substituted alkyl group and a substituted or unsubstituted heterocycle, and R 1 and R 2 are hydrogen. Represents an atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and Ar 8 represents a substituted or unsubstituted arylene group. ]
JP856693A 1993-01-21 1993-01-21 Image forming apparatus Pending JPH06222588A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP856693A JPH06222588A (en) 1993-01-21 1993-01-21 Image forming apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP856693A JPH06222588A (en) 1993-01-21 1993-01-21 Image forming apparatus

Publications (1)

Publication Number Publication Date
JPH06222588A true JPH06222588A (en) 1994-08-12

Family

ID=11696619

Family Applications (1)

Application Number Title Priority Date Filing Date
JP856693A Pending JPH06222588A (en) 1993-01-21 1993-01-21 Image forming apparatus

Country Status (1)

Country Link
JP (1) JPH06222588A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001110570A (en) * 1999-07-30 2001-04-20 Sony Corp Organic field light emitting element
US6573017B2 (en) 2000-12-18 2003-06-03 Kyocera Mita Corporation Single-layer type electrophotosensitive material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001110570A (en) * 1999-07-30 2001-04-20 Sony Corp Organic field light emitting element
US6573017B2 (en) 2000-12-18 2003-06-03 Kyocera Mita Corporation Single-layer type electrophotosensitive material

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