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JP3164426B2 - Acrylic or methacrylic acid ester having novel triphenylamine skeleton, novel polymer obtained therefrom, and electrophotographic photoreceptor using the polymer - Google Patents

Acrylic or methacrylic acid ester having novel triphenylamine skeleton, novel polymer obtained therefrom, and electrophotographic photoreceptor using the polymer

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Publication number
JP3164426B2
JP3164426B2 JP17381792A JP17381792A JP3164426B2 JP 3164426 B2 JP3164426 B2 JP 3164426B2 JP 17381792 A JP17381792 A JP 17381792A JP 17381792 A JP17381792 A JP 17381792A JP 3164426 B2 JP3164426 B2 JP 3164426B2
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JP
Japan
Prior art keywords
group
formula
substituted
integer
hydrogen
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.)
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JP17381792A
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Japanese (ja)
Other versions
JPH05202135A (en
Inventor
宏 田村
俊夫 深貝
直志 三島
正臣 佐々木
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Ricoh Co Ltd
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Ricoh Co Ltd
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  • Photoreceptors In Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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、新規なアクリル又はメ
タクリル酸エステル、それから得られたアクリル又はメ
タクリル酸エステル単独重合体又は共重合体と、該重合
体を用いた電子写真感光体に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acrylic or methacrylic acid ester, an acrylic or methacrylic acid ester homopolymer or copolymer obtained therefrom, and an electrophotographic photoreceptor using the polymer.

【0002】[0002]

【従来の技術】近年、有機感光体(OPC)が複写機、
プリンターに多く使用されている。これらOPCは電荷
発生層(CGL)、電荷移動層(CTL)を順次積層し
た構成である。CTLは低分子電荷移動材(CTM)を
バインダー樹脂中に、ある濃度で溶かし、フィルムにし
ている。CTMの添加はバインダー樹脂本来の機械的強
度を低下させ、CTLフィルムは脆く、引張強度の低い
膜である。この機械的強度低下が感光体の摩耗、傷、剥
離、クラックなどの原因と考えられる。一方、ポリビニ
ルカルバゾール、ポリビニルアントラセン、ポリビニル
ピレンなどの高分子電荷移動剤を単独CTLとして用い
た感光体が多々提案されているが、機械的強度、電気的
特性が十分でない。またM.Stolkaが、J.PO
LYM.SCI.VOL.21,969にアクリル重合
体の記載があるが、移動度が遅い。’89 JAPAN
HARD COPY P.67にヒドラゾンのビニル
重合体の記載があるが、残留電位が観察される。特開平
1−115915、特開平1−141902、特開平1
−141939記載のカルバゾールの重合体は感度が遅
い。特開平1−134456、特開平1−13445
7、特開平1−134462は感度は良好であるが、残
留電位と感度変化が観察される。特開昭64−9964
は反応上制約がある。
2. Description of the Related Art In recent years, organic photoconductors (OPCs) have been used in copiers,
Often used in printers. These OPCs have a configuration in which a charge generation layer (CGL) and a charge transfer layer (CTL) are sequentially laminated. In CTL, a low molecular charge transfer material (CTM) is dissolved in a binder resin at a certain concentration to form a film. Addition of CTM lowers the intrinsic mechanical strength of the binder resin, and the CTL film is brittle and has low tensile strength. This decrease in mechanical strength is considered to be the cause of wear, scratches, peeling, cracks, etc. of the photoreceptor. On the other hand, many photoconductors using a polymer charge transfer agent such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene as a single CTL have been proposed, but their mechanical strength and electrical properties are not sufficient. M. Stolka, J. et al. PO
LYM. SCI. VOL. 21,969 describes an acrylic polymer, but has a low mobility. '89 JAPAN
HARD COPY P. 67 describes a hydrazone vinyl polymer, but a residual potential is observed. JP-A-1-115915, JP-A-1-141902, JP-A-1
The carbazole polymer described in -141939 has low sensitivity. JP-A-1-134456, JP-A-1-134445
7, JP-A-1-134462 has good sensitivity, but a residual potential and a change in sensitivity are observed. JP-A-64-9964
Has restrictions on the reaction.

【0003】[0003]

【発明が解決しようとする課題】本発明は、新規トリフ
ェニルアミン骨格を有するアクリル又はメタクリル酸エ
ステル、それから得られた新規重合体、及び該新規トリ
フェニルアミン骨格を有するアクリル又はメタクリル酸
エステル単独重合体又は共重合体を電荷移動層に含有す
る高感度、高耐久性電子写真感光体を提供することを目
的とする。
DISCLOSURE OF THE INVENTION The present invention relates to an acrylic or methacrylic ester having a novel triphenylamine skeleton, a novel polymer obtained therefrom, and an acrylic or methacrylic ester having the novel triphenylamine skeleton. An object of the present invention is to provide a high-sensitivity, high-durability electrophotographic photosensitive member containing a coalesced or copolymer in a charge transfer layer.

【0004】[0004]

【課題を解決するための手段】本発明によれば、下記化
1で表わされるアクリル又はメタクリル酸エステル
According to the present invention, there is provided an acrylic or methacrylic acid ester represented by the following formula 1.

【化1】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1 が提供され、また下記化2で表わされる繰り返し単位を
有するアクリル又はメタクリル酸エステルの単独重合体
又は共重合体(I)
Embedded image In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : an integer of 1 to 10 n 2 : an integer of 1 to 4 n 3 , n 4 : an integer of 1 to 5 m, k: 0 or 1 And an acrylic or methacrylic acid ester homopolymer or copolymer (I) having a repeating unit represented by the following formula (2):

【化2】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1 が提供され、また、導電性支持体上に、光導電層を設け
た電子写真感光体において、光導電層中に、前記のアク
リル又はメタクリル酸エステルの単独重合体又は共重合
体(I)を含有させたことを特徴とする電子写真感光体
が提供され、更に、導電性支持体上に電荷発生層、電荷
移動層を順次積層した電子写真感光体において、該電荷
移動層中に、下記化2で表わされる繰り返し単位と、下
記化3で表わされる繰り返し単位からなり、且つ下記化
2で表わされる繰り返し単位を与える前記化1で表わさ
れるモノマーを30〜90重量%含有するモノマー混合
物を重合させて得られるアクリル又はメタクリル酸エス
テル共重合体(II)を含有させたことを特徴とする電
子写真感光体
Embedded image In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : an integer of 1 to 10 n 2 : an integer of 1 to 4 n 3 , n 4 : an integer of 1 to 5 m, k: 0 or 1 Further, in an electrophotographic photoreceptor having a photoconductive layer provided on a conductive support, the photoconductive layer contains the homopolymer or copolymer (I) of the acrylic or methacrylic acid ester. An electrophotographic photoreceptor is provided, further comprising a charge generation layer and a charge transfer layer sequentially laminated on a conductive support, wherein the charge transfer layer is represented by the following formula (2). And a repeating unit represented by the following chemical formula 3 , and
Which represents a repeating unit represented by Formula 2
Mixture containing 30 to 90% by weight of the monomer to be prepared
Electrophotographic photoreceptor containing an acrylic or methacrylic acid ester copolymer (II) obtained by polymerizing a product

【化2】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1
Embedded image In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : an integer of 1 to 10 n 2 : an integer of 1 to 4 n 3 , n 4 : an integer of 1 to 5 m, k: 0 or 1

【化3】 式中、R1:水素、メチル基 R6:直鎖又は分岐の炭素数1〜20のアルキル基、置
換、未置換のアリール基、アラルキル基が提供され、更
にまた、導電性支持体上に電荷発生層、電荷移動層を順
次積層した電子写真感光体において、電荷移動層中に、
下記化2で表わされる繰り返し単位と、下記化3で表わ
される繰り返し単位と、下記化4で表わされる繰り返し
単位からなり、且つ下記化2で表わされる繰り返し単位
を与える前記化1で表わされるモノマーを30〜90重
量%、下記化3で表わされる繰り返し単位を与えるモノ
マーを20〜40重量%、下記化4で表わされる繰り返
し単位を与えるモノマーを5〜20重量%含有するモノ
マー混合物を重合させて得られるアクリル又はメタクリ
ル酸エステル共重合体(III)のイソシアネートによ
る硬化物を含有せしめたことを特徴とする電子写真感光
Embedded image In the formula, R 1 : hydrogen, a methyl group R 6 : a linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, or an aralkyl group is provided. In an electrophotographic photoreceptor in which a charge generation layer and a charge transfer layer are sequentially laminated, in the charge transfer layer,
A repeating unit represented by the following chemical formula 2, a repeating unit represented by the following chemical formula 3, and a repeating unit represented by the following chemical formula 4, and represented by the following chemical formula 2
To give 30 to 90 weight
Amount that gives a repeating unit represented by the following formula
20 to 40% by weight of the mer
Mono containing 5 to 20% by weight of a monomer giving a unit
Electrophotographic photoreceptor comprising a cured product of an acrylic or methacrylic acid ester copolymer (III) obtained by polymerizing a polymer mixture with an isocyanate

【化2】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1
Embedded image In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : an integer of 1 to 10 n 2 : an integer of 1 to 4 n 3 , n 4 : an integer of 1 to 5 m, k: 0 or 1

【化3】 式中、R1:水素、メチル基 R6:直鎖又は分岐の炭素数1〜20のアルキル基、置
換、未置換のアリール基、アラルキル基
Embedded image In the formula, R 1 : hydrogen, methyl group R 6 : linear or branched alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group, aralkyl group

【化4】 式中、R1:水素、メチル基 5 :1〜10の整数 が提供される。Embedded image Wherein R 1 is hydrogen, methyl group n 5 is an integer from 1 to 10.

【0005】以下、本発明を詳細に説明する。本発明の
前記化1で表わされるトリフェニルアミン骨格を有する
アクリル又はメタクリル酸エステルは、下記表1に反応
式で示すように、4−(N,Nジフェニルアミノ)ベン
ズアルデヒドとジエチル−メトキシベンジルホスフォネ
ートをナトリウムメチラート下反応させ、4−ジフェニ
ルアミノ−4’−メトキシスチルベンを合成し、これを
水素添加後、シリル化合物を用いてメトキシ基を加水分
解し−OHにした後アクリルクロライドをアルカリ下反
応させて合成する。
Hereinafter, the present invention will be described in detail. The acrylic or methacrylic acid ester having a triphenylamine skeleton represented by the above formula 1 of the present invention is obtained by reacting 4- (N, N-diphenylamino) benzaldehyde and diethyl-methoxybenzylphospho as shown in the following reaction formula in Table 1. The compound is reacted under sodium methylate to synthesize 4-diphenylamino-4'-methoxystilbene. After hydrogenation, the methoxy group is hydrolyzed to -OH using a silyl compound, and then acryl chloride is alkalized. Synthesize by reacting.

【表1】 また、前記加水分解後、アルカリ存在下にエピクロルヒ
ドリンなどと反応させてアルキレンオキシ鎖をのばすこ
とができる。
[Table 1] After the hydrolysis, the alkyleneoxy chain can be extended by reacting with epichlorohydrin or the like in the presence of an alkali.

【0006】本発明の前記化2で表わされる繰り返し単
位を有するアクリル又はメタクリル酸エステルの単独重
合体又は共重合体(I)は、前記、対応するアクリル又
はメタクリル酸エステルをモノマーとし、トルエン等の
溶媒に溶解し、過酸化物或いはアゾ系の開始剤の存在下
に重合反応させて得られる。該単独重合体又は共重合体
(I)の分子量は8,000〜200,000が好まし
い。次に表2に単独重合体の例を示す。
The homopolymer or copolymer (I) of the acrylic or methacrylic ester having a repeating unit represented by the formula (2) of the present invention comprises the above-mentioned corresponding acrylic or methacrylic ester as a monomer, It is obtained by dissolving in a solvent and conducting a polymerization reaction in the presence of a peroxide or an azo-based initiator. The molecular weight of the homopolymer or copolymer (I) is preferably from 8,000 to 200,000. Next, Table 2 shows examples of the homopolymer.

【0007】[0007]

【表2の(1)】 [(1) in Table 2]

【表2の(2)】 [(2) in Table 2]

【表2の(3)】 [(3) in Table 2]

【表2の(4)】 [(4) in Table 2]

【表2の(5)】 [(5) in Table 2]

【表2の(6)】 [(6) in Table 2]

【表2の(7)】 [(7) in Table 2]

【表2の(8)】 [(8) in Table 2]

【表2の(9)】 [(9) in Table 2]

【0008】これら重合体は高い移動度を示し、高感
度、残留電位の低い電気特性を示し、フィルム性の良好
な膜である。フィルムはトルエンなどの溶媒に溶かして
CGL上に塗工して単独のCTL層として設けることが
できる。Stolkaらは、ポリメチルメタクリレート
にトリフェニルアミンを置換した膜は脆いことを報告し
ているが、本発明の重合体はアクリルのビニル鎖からの
距離が(CnH2nO)、フェニル基、(CnH2n)
などの基によって離されており、さらにアクリル基の置
換位置によって脆さ、可とう性の問題は解決される。更
に化1で示されるモノマーは他ビニルモノマー、例えば
アクリル又はメタクリル酸エステルと共重合させてフィ
ルム特性の向上を図ることができる。このような重合体
としては、前記化2で表わされるトリフェニルアミン骨
格を有する繰り返し単位と、前記化3で表わされる繰り
返し単位とを有するアクリル又はメタクリル酸エステル
と共重合体(II)、或いは更に前記化4で表わされる
繰り返し単位とを有するアクリル又はメタクリル酸エス
テル共重合体(III)が挙げられる。
These polymers exhibit high mobility, high sensitivity, low residual potential, and good film properties. The film can be provided as a single CTL layer by dissolving in a solvent such as toluene and coating on CGL. Stolka et al. Report that a film obtained by replacing triphenylamine with polymethyl methacrylate is brittle, but the polymer of the present invention has a distance from the acrylic vinyl chain of (CnH2nO), a phenyl group, (CnH2n).
And the like, and the problem of brittleness and flexibility can be solved by the substitution position of the acrylic group. Further, the monomer represented by Chemical Formula 1 can be copolymerized with another vinyl monomer, for example, an acrylic or methacrylic acid ester to improve the film properties. Examples of such a polymer include an acrylic or methacrylic acid ester having a repeating unit having a triphenylamine skeleton represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3, and a copolymer (II), or An acrylic or methacrylic acid ester copolymer (III) having a repeating unit represented by the above formula (4).

【0009】前記化3で表わされる繰り返し単位を与え
る共重合モノマーとしてはメチルアクリレート、メチル
メタクリレート、エチルアクリレート、エチルメタクリ
レート、n−ブチルアクリレート、n−ブチルメタクリ
レート、iso−ブチルアクリレート、iso−ブチル
メタクリレート、プロピルアクリレート、プロピルメタ
クリレート、ヘキシルアクリレート、ヘキシルメタクリ
レート、シクロヘキシルアクリレート、シクロヘキシル
メタクリレート、ベンジルアクリレート、ベンジルメタ
クリレート、2,2,2−トリフルオロエチルメタクリ
レート、オクタフルオロペンチルメタクリレート、ヘプ
タデカフルオロメタクリレート、フェニルメタクリレー
ト、メトキシエチルメタクリレート、エトキシエチルメ
タクリレート等が挙げられる。
Examples of the copolymerizable monomer which gives the repeating unit represented by the above formula (3) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, Propyl acrylate, propyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, 2,2,2-trifluoroethyl methacrylate, octafluoropentyl methacrylate, heptadecafluoro methacrylate, phenyl methacrylate, methoxyethyl Methacrylate, ethoxyethyl methacrylate, etc. It is below.

【0010】これらモノマーは単一あるいは複数で共重
合させてもよく、フィルム物性であるフィルム性、可撓
性、接着性、相溶性(透明性)、機械的強度として耐摩
耗性を考慮して硬度、低摩擦係数、表面エネルギー、他
として耐オゾン性、耐光性、耐湿度依存性、電気特性な
どの点から共重合モノマーの種類、単一あるいは複数、
あるいはその数、比率が決定されるが、前記化2が表わ
される繰り返し単位と、該化3で表わされる繰り返し単
位とを有する共重合体(II)において、その原料であ
る該化2で表わされる繰り返し単位を与える前記化1で
表わされるモノマーは、一般に30重量%以上、90重
量%以下が好ましい。30重量%未満であると感光体に
使用した場合感度が低下し、90重量%より多いとフィ
ルムの物性、例えば接着性、可撓性が劣化する。共重合
法はラジカルを使用した溶液重合、乳化重合、ビーズ状
重合体を得る懸濁重合また、アニオン、カチオンなどの
イオンを用いたイオン重合などが適用される。
[0010] These monomers may be copolymerized singly or in plurals, taking into consideration the film physical properties such as film properties, flexibility, adhesion, compatibility (transparency), and mechanical strength in consideration of wear resistance. In terms of hardness, low friction coefficient, surface energy, ozone resistance, light resistance, humidity resistance, electrical properties, etc.
Alternatively, the number and ratio thereof are determined. In a copolymer (II) having a repeating unit represented by the above formula (2) and a repeating unit represented by the above formula (3), the copolymer (II) is used as the starting material. The monomer represented by the above formula (1) which gives a repeating unit is generally preferably at least 30% by weight and at most 90% by weight. If the amount is less than 30% by weight, the sensitivity is reduced when used for a photoreceptor, and if it is more than 90% by weight, the physical properties of the film, for example, adhesiveness and flexibility are deteriorated. As the copolymerization method, solution polymerization using radicals, emulsion polymerization, suspension polymerization for obtaining a bead polymer, and ionic polymerization using ions such as anions and cations are applied.

【0011】前記化4が表わされる繰り返し単位を与え
る共重合モノマーとしては2−ヒドロキシエチルアクリ
レート、2−ヒドロキシエチルメタクリレート、2−ヒ
ドロキシプロピルアクリレート、2−ヒドロキシプロピ
ルメタクリレート、3−ヒドロキシプロピルアクリレー
ト、3−ヒドロキシプロピルメタクリレート等が挙げら
れる。
The copolymerizable monomer giving a repeating unit represented by the above formula (4) is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, Hydroxypropyl methacrylate and the like.

【0012】該化4で表わされるヒドロキシ基を有する
繰り返し単位を更に有する共重合体(III)におい
て、その原料である前記化1で表わされるモノマーは、
30〜90重量%が好ましく、前記化3で表わされる繰
り返し単位を与えるモノマーは20〜40重量%、又前
記化4で表わされる繰り返し単位を与えるモノマーは5
〜20重量%が好ましい。該化1で表わされるモノマー
が30重量%未満であると感光体に使用した場合感度が
低下し、90重量%より多いと接着性、可撓性が劣化す
る。前記化3で表わされる繰り返し単位はフィルムの可
撓性を付与し、該繰り返し単位を与えるモノマーが20
重量%未満であるとフィルムが脆くなり、40重量%よ
り多いと柔らかくなりフィルム性が劣化する。該化4で
表わされる繰り返し単位を与えるモノマーが5重量%未
満であると接着性が悪く、又、イソシアネート化合物と
の反応部位が少ないため、フィルム硬度が低く、耐摩耗
性が悪い。又20重量%より多いと感光体に使用した際
感度が低下する。これらヒドロキシ基をもつモノマーと
の共重合体(III)は官能基の−OHとイソシアネー
トとの架橋反応によって膜の機械的強度向上が測れる。
重合法は前記した方法と同様に共重合させる。
In the copolymer (III) which further has a repeating unit having a hydroxy group represented by the chemical formula 4, the monomer represented by the chemical formula 1 as a raw material thereof is:
The content of the repeating unit represented by the above formula (3) is preferably from 20 to 40% by weight, and the amount of the monomer providing the repeating unit represented by the above formula (5) is 5 to 90% by weight.
-20% by weight is preferred. If the amount of the monomer represented by Chemical Formula 1 is less than 30% by weight, the sensitivity decreases when the monomer is used for a photoreceptor, and if it exceeds 90% by weight, adhesiveness and flexibility deteriorate. The repeating unit represented by the above formula (3) gives the flexibility of the film, and the monomer giving the repeating unit is 20.
If it is less than 40% by weight, the film becomes brittle, and if it is more than 40% by weight, it becomes soft and the film properties deteriorate. If the amount of the monomer giving the repeating unit represented by the formula (4) is less than 5% by weight, the adhesiveness is poor, and the number of reactive sites with the isocyanate compound is small, so that the film hardness is low and the abrasion resistance is poor. On the other hand, when the content is more than 20% by weight, the sensitivity decreases when used for a photoreceptor. In the copolymer (III) with the monomer having a hydroxy group, the mechanical strength of the film can be measured by the crosslinking reaction between the functional group -OH and the isocyanate.
The polymerization is carried out in the same manner as described above.

【0013】本発明において、架橋反応に使用するイソ
シアネートは公知のものが使用でき、たとえば下記化5
で示されるイソシアネートが例示される。
In the present invention, known isocyanates can be used for the crosslinking reaction.
Is exemplified.

【化5】R7〔(R8)n’(NCO)n”〕 式中、R7:炭素数3〜20のアルキル基、炭素数3〜
20のアルコキシ基、アリール基、アラルキル基、 R8:炭素数3〜20のアルキル基、炭素数3〜20の
アルコキシ基、アリール基、アラルキル基。これら基は
直接R7に結合しているか、又は−NHCO−の結合を
介してもよい。 n’:0〜3 n”:2〜3を示す。
Embedded image R 7 [(R 8 ) n ′ (NCO) n ″] wherein R 7 is an alkyl group having 3 to 20 carbon atoms and 3 to 20 carbon atoms.
20 alkoxy groups, aryl groups, aralkyl groups, R 8 : an alkyl group having 3 to 20 carbon atoms, an alkoxy group, an aryl group, and an aralkyl group having 3 to 20 carbon atoms. These groups may be via either directly bonded to R 7, or -NHCO- bond. n ′: 0 to 3 n ″: 2 to 3

【0014】具体的にはトルイレンジイソシアネート、
3,3’−ジメチル−1−ジフェニル−4,4’−ジイ
ソシアネート、ジフェニールメタン4,4’−ジイソシ
アネート、トリフェニルメタントリイソシアネート、ま
た住友バイエル(株)から市販されているスミジュール
L、HL、VL、Nなどのポリイソシアネート化合物、
武田薬品から市販されているタケネート500、大日本
インキから市販されているバーノックD−750などの
架橋イソシアネートが例示される。本発明において、イ
ソシアネート化合物は、共重合体(III)中の水酸基
と等量添加することが好ましいが、もちろん多くても少
なくてもよい。一般には共重合体(III)10重量部
に対して0.05〜2重量部を塗工まえにトルエンなど
の芳香族系溶媒、MEKなどのケトン系溶媒で溶解し、
90〜150℃で乾燥、硬化する。
Specifically, tolylene diisocyanate,
3,3'-dimethyl-1-diphenyl-4,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, triphenylmethane triisocyanate, and Sumidur L, HL commercially available from Sumitomo Bayer KK , VL, N and other polyisocyanate compounds;
Crosslinked isocyanates such as Takenate 500 commercially available from Takeda Pharmaceutical Co., and Vernock D-750 commercially available from Dainippon Ink. In the present invention, the isocyanate compound is preferably added in the same amount as the hydroxyl group in the copolymer (III), but may be more or less. Generally, 0.05 to 2 parts by weight based on 10 parts by weight of the copolymer (III) is dissolved in an aromatic solvent such as toluene or a ketone solvent such as MEK before coating.
Dry and cure at 90-150 ° C.

【0015】感光体は電荷発生層、電荷移動層を順次積
層した負帯電型感光体、電荷移動層、電荷発生層を順次
積層した正帯電型感光体、単層の正帯電型感光体などの
層構成があり本発明の重合体はそれらの全てに適応され
る。電荷発生材料としてはC.I.No.59300バ
ットオレンジ3などの縮合多環キノン化合物、C.I.
No.38001などのペリレン化合物、およびカルバ
ゾール骨格を有するアゾ顔料(特開昭53−95033
号公報に記載)、スチリルスチルベン骨格を有するアゾ
顔料(特開昭53−138229号公報に記載)、トリ
フェニルアミン骨格を有するアゾ顔料(特開昭53−1
32547号公報に記載)、ジベンゾチオフェン骨格を
有するアゾ顔料(特開昭54−21728号公報に記
載)、オキサジアゾール骨格を有するアゾ顔料(特開昭
54−12742号公報に記載)、フルオレノン骨格を
有するアゾ顔料(特開昭54−22834号公報に記
載)、ビススチルベン骨格を有するアゾ顔料(特開昭5
4−17733号公報に記載)、ジスチリルオキサジア
ゾール骨格を有するアゾ顔料(特開昭54−2129号
公報に記載)、ジスチリルカルバゾール骨格を有するア
ゾ顔料(特開昭54−17734号公報に記載)、カル
バゾール骨格を有するトリアゾ顔料(特開昭57−19
5767号公報に記載)、アントラキノン骨格を有する
アゾ顔料(特開昭57−202545号公報に記載)、
金属あるいは、無金属フタロシアニン、スクエリアム染
料を挙げることができる。
The photoreceptor includes a negatively charged photoreceptor in which a charge generation layer and a charge transfer layer are sequentially laminated, a positively chargeable photoreceptor in which a charge transfer layer and a charge generation layer are sequentially laminated, and a single layer positively chargeable photoreceptor. There is a layer configuration and the polymers of the invention are adapted to all of them. C.I. I. No. Fused polycyclic quinone compounds such as 59300 Vat Orange 3; I.
No. And azo pigments having a carbazole skeleton (JP-A-53-95033).
Azo pigments having a styrylstilbene skeleton (described in JP-A-53-138229) and azo pigments having a triphenylamine skeleton (described in JP-A-53-1).
32547), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), fluorenone skeleton Azo pigments having a bisstilbene skeleton (described in JP-A-54-22834).
4-17733), an azo pigment having a distyryloxadiazole skeleton (described in JP-A-54-2129), and an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-17834). Described), triazo pigments having a carbazole skeleton (JP-A-57-19)
No. 5767), an azo pigment having an anthraquinone skeleton (described in JP-A-57-202545),
Metal or metal-free phthalocyanine and squarium dye can be mentioned.

【0016】これら電荷発生材は単独、もしくはバイン
ダー樹脂と共にボールミル、アトライター、振動ミルな
どの方法で粉砕、分散する。溶剤としてはメタノール、
イソプロピルアルコールなどのアルコール類、アセト
ン、メチルエチルケトン、シクロヘキサノンなどのケト
ン類、テトラヒドロフラン、ジオキサン、エチレングリ
コールジアルキルエーテルなどのエーテル類、酢酸エチ
ル、酢酸ブチルなどのエステル類、塩化メチレン、ジク
ロロエタン、クロロベンゼンなどのハロゲン化炭化水
素、ベンゼン、トルエン、キシレンなどの芳香族炭化水
素などが挙げられ、これら二種以上の混合物としても使
用できる。バインダー樹脂としてはポリビニルブチラー
ル、ポリビニルアセタール、セルロース誘導体、フェノ
ール樹脂、エポキシ樹脂、アクリル系樹脂、ポリエステ
ル、シリコーン樹脂、ポリ酢酸ビニル、等が挙げられ
る。粉砕、分散は顔料平均粒径が0.3μm以下が好ま
しい。
These charge generating materials are used alone or together with a binder resin to be pulverized and dispersed by a method such as a ball mill, an attritor, and a vibration mill. Methanol as a solvent,
Alcohols such as isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as tetrahydrofuran, dioxane, ethylene glycol dialkyl ether, esters such as ethyl acetate and butyl acetate, and halogenation such as methylene chloride, dichloroethane and chlorobenzene Examples thereof include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and can also be used as a mixture of two or more of these. Examples of the binder resin include polyvinyl butyral, polyvinyl acetal, a cellulose derivative, a phenol resin, an epoxy resin, an acrylic resin, a polyester, a silicone resin, and polyvinyl acetate. Pulverization and dispersion preferably have an average pigment particle size of 0.3 μm or less.

【0017】電荷発生層の塗工法は、浸漬法、スプレー
法、ロール法などの従来公知の方法が適用される。膜厚
は0.05〜5μmで好ましくは0.05〜1μmであ
る。
As a method for coating the charge generation layer, a conventionally known method such as a dipping method, a spray method, or a roll method is applied. The film thickness is 0.05 to 5 μm, preferably 0.05 to 1 μm.

【0018】また、分散液中にバインダー樹脂を含有し
ない場合は導電性支持体からの電荷注入防止のため、中
間層を設けることが好ましく、中間層用バインダー樹脂
としてポリアミド、ポリアクリルアニリド、カゼイン、
塩ビ−酢ビ−マレイン酸共重合体、フェノール樹脂等が
挙げられる。
When a binder resin is not contained in the dispersion, an intermediate layer is preferably provided in order to prevent charge injection from the conductive support, and polyamide, polyacrylanilide, casein, and the like are used as the binder resin for the intermediate layer.
Examples thereof include polyvinyl chloride-vinyl acetate-maleic acid copolymer and phenol resin.

【0019】CTLは重合体(I)、(II)、(II
I)をトルエンなどの芳香族炭化水素、塩化メチレンな
どのハロゲン化炭化水素、テトラヒドロフランなどの環
状エーテルに溶解し、浸漬法、スプレー法、ロール法で
塗工して膜厚10〜50μmで設ける。また重合体
(I)は他のバインダー樹脂との併用もでき、併用され
るバインダー樹脂としてはポリスチレン、スチレン−M
MA共重合体、スチレン−ブタジエン共重合体、水素化
スチレン−ブタジエン共重合体、ポリMMA、ポリエス
テル、ポリカーボネート、ポリアリレート、ポリスルフ
ォン、ポリフェニレンオキシドなどのフィルム性の良好
な樹脂と併用される。混合比率は重合体(I)10重合
部に対して2〜10重合部が良好である。
CTLs are polymers (I), (II) and (II)
I) is dissolved in an aromatic hydrocarbon such as toluene, a halogenated hydrocarbon such as methylene chloride, or a cyclic ether such as tetrahydrofuran, and applied by a dipping method, a spray method, or a roll method to form a film having a thickness of 10 to 50 μm. The polymer (I) can be used in combination with another binder resin, and the binder resin used in combination is polystyrene, styrene-M
It is used in combination with a resin having good film properties such as MA copolymer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, polyMMA, polyester, polycarbonate, polyarylate, polysulfone, and polyphenylene oxide. The mixing ratio is preferably 2 to 10 polymer parts for 10 polymer parts of the polymer (I).

【0020】また、重合体(I)、(II)、(II
I)に低分子電荷移動材を溶解してCTLを形成するこ
ともでき、電荷移動材としてはピラゾリン系化合物、α
−フェニルスチルベン系化合物、ヒドラゾン系化合物、
ジアリールメタン系化合物、トリフェニルアミン系化合
物、ジビニルベンゼン系化合物、オキサジアゾール系化
合物、ジアミノカルバゾール系化合物等が挙げられる。
The polymers (I), (II) and (II)
The CTL can also be formed by dissolving a low-molecular charge transfer material in I), and the charge transfer material may be a pyrazoline compound, α
-A phenylstilbene compound, a hydrazone compound,
Examples include a diarylmethane-based compound, a triphenylamine-based compound, a divinylbenzene-based compound, an oxadiazole-based compound, and a diaminocarbazole-based compound.

【0021】以下実施例を示す。 実施例1 4ージフェニルアミノ−4’−メトキシスチルベン 4−ジフェニルアミノべンズアルデヒド54.6g
(0.2mol)、ジエチル−4−メトキシベンジルホ
スフォネート51.6g(0.2mol)、D.M.F
250mlを500ml四径フラスコに取り、攪拌下2
8%ナトリウムメチラート57.9gを室温で15分で
滴下し、50〜60℃で5時間反応し、水500mlで
希釈し、酢酸酸性とした後、濾別しウエットケーキをメ
タノール100mlで3回洗浄し、エタノール:ジオキ
サンの混合溶媒で再結晶した。黄色、針状晶m.p.1
70〜171.5℃、収量46.2g(61.3%) 1−(4−ジフェニルアミノフェニル)−2−(4
−メトキシフェニル)エタン 上記スチルベン37.7g(0.1mol)をジオキサ
ン250mlに溶解し5%Pd/C粉末4gを加え、水
素2.41で水素添加した。溶媒を除去しオイル状、透
明、淡黄色物が得られた。I.Rからδ:900〜10
00cm-1のHC=CHの吸収が消失していた。 1−(4−ジフェニルアミノフェニル)−2−(4
−ヒドロキシフェニル)エタン 上記水添化合物38.5g、スルフォラン200ml、
NaI45gを加え、四径フラスコで120℃で攪拌、
溶解し、60℃に冷却し、蒸留水2mlを加え、次いで
トリメチルクロロシラン32.6gを30分で滴下し、
60〜70℃で3時間反応し、水500ml中へ注ぎ、
茶褐色タール物を得る。それを水200mlで数回洗浄
し、トルエン300mlに溶解し褐色トルエン溶液を得
る。これを亜硫酸ナトリウムの飽和水溶液、100ml
で2回洗浄し淡黄色、透明トルエン溶液が得られた。無
水MgSO4で脱水後、溶媒除去しシリカゲル、トルエ
ンを用いてクロマト分離して加水分解物を得た。オイル
状物31.4g。I.RνOH3550,3400cm
-1 1−〔2’−(4”−ジフェニルアミノフェニル)
エチル〕フェニルメタクリレート 上記加水分解物31.4g、ジオキサン150ml、2
0%水酸化ナトリウム水溶液20gを取り、5℃に冷却
し攪拌下メタクリルクロライド10.8gを滴下した。
温度は10℃以下に保ち、滴下終了後、室温で2時間反
応し水500ml中に注ぎ、トルエン300mlで抽出
し、水200mlで2回洗浄後、抽出液を無水MgSO
4で脱水し、溶媒除去後シリカゲル、トルエンを用いて
クロマト分離してモノマーを得た。m.p:105.5
〜107℃、30g、I.Rν:3550,3400c
-1の消失と共に1740cm-1にC=O、950cm
-1に=CH2の吸収が観察された。
Examples will be described below. Example 1 44.6 g of 4-diphenylamino-4'-methoxystilbene 4-diphenylaminobenzaldehyde
(0.2 mol), 51.6 g (0.2 mol) of diethyl-4-methoxybenzylphosphonate, D.I. M. F
Transfer 250 ml to a 500 ml four-necked flask,
57.9 g of 8% sodium methylate was added dropwise at room temperature for 15 minutes, reacted at 50-60 ° C. for 5 hours, diluted with 500 ml of water, acidified with acetic acid, filtered, and the wet cake was filtered three times with 100 ml of methanol. It was washed and recrystallized with a mixed solvent of ethanol and dioxane. Yellow, needles m.p. p. 1
70-171.5 ° C, yield 46.2 g (61.3%) 1- (4-diphenylaminophenyl) -2- (4
-Methoxyphenyl) ethane 37.7 g (0.1 mol) of the above stilbene was dissolved in 250 ml of dioxane, 4 g of 5% Pd / C powder was added, and hydrogenation was performed with 2.41 hydrogen. The solvent was removed to obtain an oily, transparent, pale yellow substance. I. From R δ: 900 to 10
The absorption of HC = CH at 00 cm -1 had disappeared. 1- (4-diphenylaminophenyl) -2- (4
-Hydroxyphenyl) ethane 38.5 g of the above hydrogenated compound, 200 ml of sulfolane,
Add 45 g of NaI and stir at 120 ° C. in a four-diameter flask,
Dissolve, cool to 60 ° C., add 2 ml of distilled water, then add 32.6 g of trimethylchlorosilane in 30 minutes,
React at 60-70 ° C. for 3 hours, pour into 500 ml of water,
A brown tar is obtained. It is washed several times with 200 ml of water and dissolved in 300 ml of toluene to obtain a brown toluene solution. 100 ml of a saturated aqueous solution of sodium sulfite
, And a pale yellow, transparent toluene solution was obtained. After dehydration over anhydrous MgSO 4 , the solvent was removed, and the residue was chromatographed using silica gel and toluene to obtain a hydrolyzate. 31.4 g of oily substance. I. RνOH 3550, 3400cm
-1 1- [2 '-(4 "-diphenylaminophenyl)
[Ethyl] phenyl methacrylate 31.4 g of the above hydrolyzate, 150 ml of dioxane, 2
20 g of a 0% aqueous sodium hydroxide solution was taken, cooled to 5 ° C., and 10.8 g of methacryl chloride was added dropwise with stirring.
The temperature was kept at 10 ° C. or lower. After the completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours, poured into 500 ml of water, extracted with 300 ml of toluene, washed twice with 200 ml of water, and extracted with anhydrous MgSO 4.
After dehydration in 4 and removal of the solvent, chromatography separation was performed using silica gel and toluene to obtain a monomer. m. p: 105.5
~ 107 ° C, 30 g, I.V. Rν: 3550, 3400c
C = O at 1740 cm -1 with disappearance of m -1 , 950 cm
= Absorption of CH 2 were observed to -1.

【0022】実施例2 1−(4−ジフェニルアミノフェニル)−2−
(4’−3”−ヒドロキシプロポキシフェニル)エタン 実施例1−のヒドロキシ体36.5g、20%水酸化
ナトリウム水溶液24g、ジオキサン200mlを50
℃に加熱攪拌下、エピクロロヒドリン11.1gを30
分で滴下し、60℃で5時間反応後水500ml中へ注
ぎ、油相をトルエンで抽出し、水200mlで2回洗浄
後、無水MgSO4で脱水しシリカゲル、展開溶媒トル
エンでカラムクロマト分離した。無水オイル状20gを
得た。47.28% γ−{4−〔2−(4−ジフェニルアミノフェニ
ル)エチル〕}フェニルオキシプロピルメタクリレート 上記アルコール前駆体20gをジオキサン150mlに
溶解し、ピリジン4mlを取り、5℃に冷却し攪拌下メ
タクリルクロライド5.9gを滴下した。滴下後2時間
反応し、水300ml中へ注ぎトルエン200mlで抽
出して、水200mlで2回洗浄し、無水MgSO4
脱水後シリカゲル、トルエンでカラムクロマト分離して
無色オイル状モノマー19gを得た。82.0%
Example 2 1- (4-diphenylaminophenyl) -2-
(4′-3 ″ -Hydroxypropoxyphenyl) ethane 36.5 g of the hydroxy compound of Example 1, 24 g of a 20% aqueous sodium hydroxide solution, and 200 ml of dioxane were added to 50
While heating and stirring at 11.degree. C., 11.1 g of epichlorohydrin was added to 30.
After the reaction at 60 ° C. for 5 hours, the mixture was reacted at 60 ° C. for 5 hours, poured into 500 ml of water, the oil phase was extracted with toluene, washed twice with 200 ml of water, dehydrated with anhydrous MgSO 4 , and separated by silica gel and column chromatography with a developing solvent toluene. . 20 g of anhydrous oil was obtained. 47.28% γ- {4- [2- (4-diphenylaminophenyl) ethyl]} phenyloxypropyl methacrylate 20 g of the above alcohol precursor is dissolved in 150 ml of dioxane, 4 ml of pyridine is taken, cooled to 5 ° C. and stirred. Methacryl chloride (5.9 g) was added dropwise. After dropping, the mixture was reacted for 2 hours, poured into 300 ml of water, extracted with 200 ml of toluene, washed twice with 200 ml of water, dehydrated with anhydrous MgSO 4 , and separated by silica gel and column chromatography with toluene to obtain 19 g of a colorless oily monomer. . 82.0%

【0023】実施例3 ポリ−4−〔2’−(4”−ジフェニルアミノフェニ
ル)エチル〕フェニルメタクリレート(表2 重合体N
o.26) 上記モノマー25g、トルエン50g、アゾビスイソブ
チルニトリル0.09gを加え、室温、窒素気流下1時
間攪拌後、60℃で5時間、70℃で2時間、80℃で
2時間、100℃で1時間重合反応した。反応液をメタ
ノール2Lに滴下し、重合体を晶析させ、析出物をアセ
トン500mlで洗浄後、再度重合体をトルエン300
mlに溶解し、メタノール2Lで再沈を繰返した。収量
18g(72%)
Example 3 Poly-4- [2 '-(4 "-diphenylaminophenyl) ethyl] phenyl methacrylate (Table 2 Polymer N
o. 26) 25 g of the above monomer, 50 g of toluene and 0.09 g of azobisisobutylnitrile were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen stream, then at 60 ° C for 5 hours, at 70 ° C for 2 hours, at 80 ° C for 2 hours, and at 100 ° C. The polymerization reaction was performed for 1 hour. The reaction solution was added dropwise to 2 L of methanol to crystallize the polymer, and the precipitate was washed with 500 ml of acetone.
The solution was dissolved in 2 ml of methanol, and reprecipitation was repeated with 2 L of methanol. Yield 18 g (72%)

【0024】実施例4 ポリ−γ−{4−〔2−(4−ジフェニルアミノフェニ
ル)エチル〕}フェニルオキシプロピルメタクリレート
(表2 重合体No.43) 重合は全て実施例3と同様におこなったが、G.P.C
の結果から分子量は5,000〜10万で得られた。こ
れはモノマーの立体障害、ビニル基の電子密度、反応雰
囲気の微妙な違いによるものと考えられる。分子量の違
いは電気特性に大きく影響せず、むしろ置換基、置換位
置の効果が大きく影響する。
Example 4 Poly-γ- {4- [2- (4-diphenylaminophenyl) ethyl]} phenyloxypropyl methacrylate (Table 2 polymer No. 43) All polymerizations were carried out in the same manner as in Example 3. Is G. P. C
As a result, a molecular weight of 5,000 to 100,000 was obtained. This is thought to be due to steric hindrance of the monomer, electron density of the vinyl group, and subtle differences in the reaction atmosphere. The difference in the molecular weight does not significantly affect the electrical properties, but rather the effects of the substituents and substitution positions.

【0025】実施例5 表2の重合体No.3のモノマー20g、n−ブチルメ
タクリレート(nBMA)7g、アゾビスイソブチロニ
トリル(AIBN)0.09g、トルエン63gを四径
フラスコに取り、窒素ガスを室温で1時間バブリング
後、60℃で5時間、70℃で2時間、80℃で4時間
反応した。反応液は淡茶色の粘稠であった。この反応液
をトルエン200mlで希釈して、メタノール2L中へ
滴下して析出し、析出物をアセトン500mlで洗浄し
て、再度トルエン200mlに溶解しメタノールで再沈
して重合物を得た。
Example 5 Polymer No. 2 in Table 2 20 g of the monomer of No. 3, n-butyl methacrylate (nBMA) 7 g, azobisisobutyronitrile (AIBN) 0.09 g, and toluene 63 g were placed in a four-necked flask, and nitrogen gas was bubbled at room temperature for 1 hour. The reaction was carried out at 70 ° C. for 2 hours and at 80 ° C. for 4 hours. The reaction solution was light brown and viscous. The reaction solution was diluted with 200 ml of toluene, and dropped into 2 L of methanol to precipitate. The precipitate was washed with 500 ml of acetone, dissolved again in 200 ml of toluene, and reprecipitated with methanol to obtain a polymer.

【0026】実施例6 表2の重合体No.19のモノマー20g、メチルメタ
クリレート(MMA)5g、nBMA5g、AIBN
0.1g、トルエン70gを四径フラスコに取り、実施
例5と同様にして重合物を得た。
Example 6 Polymer No. 2 in Table 2 20 g of 19 monomer, 5 g of methyl methacrylate (MMA), 5 g of nBMA, AIBN
0.1 g and 70 g of toluene were placed in a four-diameter flask, and a polymer was obtained in the same manner as in Example 5.

【0027】実施例7 表2の重合体No.27のモノマー20g、nBMA5
g、MMA2g、2ヒドロキシエチルメタクリレート
(2HEMA)3g、AIBN0.1g、トルエン70
gを四径フラスコに取り、実施例5と同様にして重合反
応を行ない、固形分30%の淡茶色の粘稠液を得た。
Example 7 Polymer No. 2 shown in Table 2 20 g of monomer 27, nBMA5
g, MMA 2 g, 2-hydroxyethyl methacrylate (2HEMA) 3 g, AIBN 0.1 g, toluene 70
g was placed in a four-diameter flask and subjected to a polymerization reaction in the same manner as in Example 5 to obtain a pale brown viscous liquid having a solid content of 30%.

【0028】表2の重合体No.35のモノマー20
g、2エチルヘキシルメタクリレート(2HEMA)5
g、ベンジルメタクリレート(BzyMA)4g、2ヒ
ドロキシプロピルメタクリレート4g、AIBN0.1
2g、トルエン77gを四径フラスコに取り、実施例5
と同様にして重合反応を行ない、固形分30%の淡茶色
の粘稠液を得た。以上の様にして共重合体(II)及び(II
I)が得られるが、実施例7,8の共重合体は再沈せず、
このまま塗工液にした。
The polymer Nos. 35 monomers 20
g, 2 ethylhexyl methacrylate (2HEMA) 5
g, benzyl methacrylate (BzyMA) 4 g, 2-hydroxypropyl methacrylate 4 g, AIBN 0.1
Example 5 5 g of 2 g and 77 g of toluene were placed in a four-diameter flask.
A polymerization reaction was carried out in the same manner as described above to obtain a pale brown viscous liquid having a solid content of 30%. As described above, the copolymers (II) and (II)
Although I) was obtained, the copolymers of Examples 7 and 8 did not reprecipitate,
The coating solution was used as it was.

【0029】実施例9 0.3mmのアルミ板上にドクターブレードで下記の中
間層液を塗工し、120℃で乾燥して0.3μmの中間
層を設けた。 ポリアミド樹脂(CM−8000 東レ社製) 4部 メタノール 60部 ブタノール 36部 次いで、下記電荷発生層塗工液を調整しブレード法で塗
工し、120℃、10分間乾燥し、0.3μmの膜厚の
電荷発光層を設けた。 〔電荷発生層塗工液〕 下記化6で表わされる化合物 22部 シクロヘキサノン 440部
Example 9 The following intermediate layer solution was coated on a 0.3 mm aluminum plate with a doctor blade and dried at 120 ° C. to provide a 0.3 μm intermediate layer. Polyamide resin (CM-8000, manufactured by Toray Industries) 4 parts Methanol 60 parts Butanol 36 parts Next, the following charge generation layer coating solution was prepared, coated by a blade method, dried at 120 ° C. for 10 minutes, and dried to a 0.3 μm film. A thick light emitting layer was provided. [Charge Generating Layer Coating Solution] 22 parts of a compound represented by the following formula 6 440 parts of cyclohexanone

【化6】 をボールミルで72時間粉砕、分散して、600部のシ
クロヘキサノンを加え再度3時間ボールミル後、シクロ
ヘキサノン:メチルエチルケトン=1:1重量比の混合
溶媒800部でレットダウンし塗工液とした。次いで、
上記電荷発生層上に下記電荷移動層液を調整しブレード
法で塗工し、120℃、20分間乾燥し、膜厚23μm
の電荷移動層を設けた。 表2のNo.1の重合体 Mn=23,000 5部 トルエン 5部
Embedded image Was ground and dispersed in a ball mill for 72 hours, and 600 parts of cyclohexanone was added. After ball milling for 3 hours again, the mixture was let down with 800 parts of a mixed solvent of cyclohexanone: methyl ethyl ketone = 1: 1 by weight to obtain a coating liquid. Then
The following charge transfer layer liquid was prepared on the charge generation layer, applied by a blade method, dried at 120 ° C. for 20 minutes, and had a thickness of 23 μm.
Was provided. No. of Table 2 Polymer 1 Mn = 23,000 5 parts Toluene 5 parts

【0030】実施例10〜22 実施例9と同様に中間層、電荷発生層を設けた上に表2
に示した化合物を塗工して感光体を作成した。
Examples 10 to 22 As in Example 9, an intermediate layer and a charge generation layer were provided, and
Were coated to prepare a photoreceptor.

【0031】以上の様にして作成した電子写真感光体を
静電複写紙試験装置〔(株)川口電機製作所製SP42
8型〕を使用し、以下の条件で電子写真特性を評価した
(ダイナミックモードで測定)。まずサンプルに−6K
Vのコロナ放電を20秒間行なって帯電せしめ、20秒
後の表面電位Vm(Volt)を測定し、更に20秒間
暗所に放置し、その時の表面電位Vo(Volt)を測
定し、ついで4.5luxの白色タングステン光を照射
し、Voが1/2、1/10に減衰するのに要する露光
量E1/2、E1/10(lux・sec)、及び照射
30秒後の表面電位Vr(Volt)を測定した。その
結果を表3に示す。
The electrophotographic photosensitive member prepared as described above is used as an electrostatic copying paper tester [SP42 manufactured by Kawaguchi Electric Co., Ltd.]
8 type], and the electrophotographic characteristics were evaluated under the following conditions (measured in a dynamic mode). First, the sample is -6K
3. Perform corona discharge of V for 20 seconds to charge, measure the surface potential Vm (Volt) after 20 seconds, leave in a dark place for further 20 seconds, measure the surface potential Vo (Volt) at that time, and then 4. Exposure amounts E1 / 2 and E1 / 10 (lux · sec) required to irradiate 5 lux of white tungsten light to reduce Vo to 1/2 and 1/10, and a surface potential Vr (Volt) 30 seconds after irradiation ) Was measured. Table 3 shows the results.

【0032】[0032]

【表3】 [Table 3]

【0033】共重合体(II)についても実施例9と同
様に感光体を作成した。表4に共重合成分、比率を記
し、その感光特性を示した。
A photoreceptor was prepared in the same manner as in Example 9 for the copolymer (II). Table 4 shows the copolymer components and ratios, and shows the photosensitive characteristics.

【表4】 [Table 4]

【0034】実施例28 実施例9と同様に中間層、電荷発生層を設けた上に実施
例23で使用した共重合体5部と下記化7で表わされる
電荷移動材1部をトルエン10部に溶解し実施例9と同
様に塗工し感光体を得た。
Example 28 An intermediate layer and a charge generation layer were provided in the same manner as in Example 9, and 5 parts of the copolymer used in Example 23 and 1 part of the charge transfer material represented by the following formula 7 were replaced with 10 parts of toluene. And coated in the same manner as in Example 9 to obtain a photoreceptor.

【化7】 Embedded image

【0035】実施例29 実施例28と同様に中間層、電荷発生層を設けた上に実
施例24で使用した共重合体5部と上記化7で表わされ
るCTM−1、1部で電荷移動層を設けた以外は実施例
9と同様に感光体を作成した。
Example 29 In the same manner as in Example 28, an intermediate layer and a charge generating layer were provided, and 5 parts of the copolymer used in Example 24 and 1 part of CTM-1 represented by the above formula 7 were used for charge transfer. A photoconductor was prepared in the same manner as in Example 9, except that a layer was provided.

【0036】実施例30 実施例26で使用した共重合体5部、下記化8で表わさ
れるCTM−2、1部で電荷移動層を設けた以外は実施
例9と同様に感光体を作成した。
Example 30 A photoconductor was prepared by the same way as that of Example 9 except that 5 parts of the copolymer used in Example 26 and 1 part of CTM-2 represented by the following formula 8 were provided with a charge transfer layer. .

【化8】 Embedded image

【0037】以上、得られた感光体について感光特性を
表5に示す。
Table 5 shows the photosensitive characteristics of the obtained photosensitive members.

【表5】 [Table 5]

【0038】実施例31 実施例9と同様に中間層、電荷発生層を積層した上に実
施例7の2HEMAを共重合した30%溶液5部、トル
イレンジイソシアネート0.1部を添加してブレード法
で塗工して130℃、30分間乾燥、硬化を行ない、電
荷移動層を設けた。
Example 31 In the same manner as in Example 9, the intermediate layer and the charge generating layer were laminated, and 5 parts of a 30% solution of 2HEMA copolymerized in Example 7 and 0.1 part of toluylene diisocyanate were added. Coating was carried out by a method, and drying and curing were performed at 130 ° C. for 30 minutes to provide a charge transfer layer.

【0039】実施例32 実施例31の実施例7を実施例8にかえた以外は同様に
して感光体を作成した。
Example 32 A photoconductor was prepared in the same manner as Example 31 except that Example 7 was replaced with Example 8.

【0040】以上、得られた感光体について感光特性を
表6に示す。
Table 6 shows the photosensitive characteristics of the obtained photoreceptor.

【表6】 実施例31,32をイソパラフィン系溶媒のアイソパー
Hまたトルエン、メチルエチルケトン溶媒に浸漬しても
膜の溶出は認められなかった。
[Table 6] When Examples 31 and 32 were immersed in Isopar H, an isoparaffin-based solvent, or a solvent of toluene or methyl ethyl ketone, no elution of the film was observed.

【0041】[0041]

【発明の効果】本発明の前記化1で表わされるトリフェ
ニルアミン骨格を有するアクリル又はメタクリル酸エス
テル、及び前記化2、または化2及び化3、または化
2、化3及び化4で表わされる繰り返し単位を有する重
合体(I)、共重合体(II)、(III)は新規であ
り、該重合体(I)、共重合体(II)、(III)
を、電子写真感光体の電荷移動層中に含有させたことに
より、高感度、高耐久性の感光体が得られるという効果
がある。
According to the present invention, an acrylic or methacrylic ester having a triphenylamine skeleton represented by the above formula (1), and represented by the above formula (2), (2) and (3), or (2), (3) and (4) The polymer (I), copolymer (II), and (III) having a repeating unit is a novel polymer (I), copolymer (II), and (III)
Is contained in the charge transfer layer of the electrophotographic photoreceptor, whereby there is an effect that a photoreceptor having high sensitivity and high durability can be obtained.

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

【図1】4−ジフェニルアミノ−4’−メトキシスチル
ベンの赤外線吸収スペクトル
FIG. 1. Infrared absorption spectrum of 4-diphenylamino-4′-methoxystilbene

【図2】1−(4−ジフェニルアミノフェニル)−2−
(4−ヒドロキシフェニル)エタンの赤外線吸収スペク
トル
FIG. 2. 1- (4-diphenylaminophenyl) -2-
Infrared absorption spectrum of (4-hydroxyphenyl) ethane

【図3】4−〔2’−(4”−ジフェニルアミノフェニ
ル)エチル〕フェニルメタクリレートの赤外線吸収スペ
クトル
FIG. 3 is an infrared absorption spectrum of 4- [2 ′-(4 ″ -diphenylaminophenyl) ethyl] phenyl methacrylate

【図4】ポリ−4−〔2’−(4”−ジフェニル)エチ
ル〕フェニメタクリレートの赤外線吸収スペクトル
FIG. 4 is an infrared absorption spectrum of poly-4- [2 ′-(4 ″ -diphenyl) ethyl] phenylmethacrylate

───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐々木 正臣 東京都大田区中馬込1丁目3番6号 株 式会社リコー内 (58)調査した分野(Int.Cl.7,DB名) C08F 20/36 C07C 217/80 C07C 219/34 G03G 5/06 - 5/07 CA,REGISTRY(STN)──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (58) Field surveyed (Int.Cl. 7 , DB name) C08F 20 / 36 C07C 217/80 C07C 219/34 G03G 5/06-5/07 CA, REGISTRY (STN)

Claims (5)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 下記化1で表わされるアクリル又はメタ
クリル酸エステル 【化1】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1
1. An acrylic or methacrylic acid ester represented by the following chemical formula 1. In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : an integer of 1 to 10 n 2 : an integer of 1 to 4 n 3 , n 4 : an integer of 1 to 5 m, k: 0 or 1
【請求項2】 下記化2で表わされる繰り返し単位を有
するアクリル又はメタクリル酸エステルの単独重合体又
は共重合体(I) 【化2】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1
2. An acrylic or methacrylic acid ester homopolymer or copolymer (I) having a repeating unit represented by the following chemical formula (2): In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : an integer of 1 to 10 n 2 : an integer of 1 to 4 n 3 , n 4 : an integer of 1 to 5 m, k: 0 or 1
【請求項3】 導電性支持体上に、光導電層を設けた電
子写真感光体において、光導電層中に、請求項2記載の
アクリル又はメタクリル酸エステルの単独重合体又は共
重合体(I)を含有させたことを特徴とする電子写真感
光体。
3. An electrophotographic photoreceptor having a photoconductive layer provided on a conductive support, wherein the photoconductive layer comprises a homopolymer or copolymer (I) of the acrylic or methacrylic acid ester according to claim 2. An electrophotographic photoreceptor characterized by containing:
【請求項4】 導電性支持体上に電荷発生層、電荷移動
層を順次積層した電子写真感光体において、該電荷移動
層中に、下記化2で表わされる繰り返し単位と、下記化
3で表わされる繰り返し単位からなり、且つ下記化2で
表わされる繰り返し単位を与える請求項1に記載の化1
で表わされるモノマーを30〜90重量%含有するモノ
マー混合物を重合させて得られるアクリル又はメタクリ
ル酸エステル共重合体(II)を含有させたことを特徴と
する電子写真感光体。 【化2】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1 【化3】 式中、R1:水素、メチル基 R6:直鎖又は分岐の炭素数1〜20のアルキル基、置
換、未置換のアリール基、アラルキル基
4. An electrophotographic photosensitive member in which a charge generation layer and a charge transfer layer are sequentially laminated on a conductive support, wherein the charge transfer layer contains a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3). Which consists of repeating units
2. A compound according to claim 1, which gives a repeating unit represented by:
Containing 30 to 90% by weight of a monomer represented by the formula:
An electrophotographic photoreceptor comprising an acrylic or methacrylic acid ester copolymer (II) obtained by polymerizing a polymer mixture . Embedded image In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : integer of 10 to 10 n 2 : integer of 1 to 4 n 3 , n 4 : integer of 1 to 5 m, k: 0 or 1 ] In the formula, R 1 : hydrogen, methyl group R 6 : linear or branched alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group, aralkyl group
【請求項5】 導電性支持体上に電荷発生層、電荷移動
層を順次積層した電子写真感光体において、電荷移動層
中に、下記化2で表わされる繰り返し単位と、下記化3
で表わされる繰り返し単位と、下記化4で表わされる繰
り返し単位からなり、且つ下記化2で表わされる繰り返
し単位を与える請求項1に記載の化1で表わされるモノ
マーを30〜90重量%、下記化3で表わされる繰り返
し単位を与えるモノマーを20〜40重量%、下記化4
で表わされる繰り返し単位を与えるモノマーを5〜20
重量%含有するモノマー混合物を重合させて得られる
クリル又はメタクリル酸エステル共重合体(III)のイ
ソシアネートによる硬化物を含有せしめたことを特徴と
する電子写真感光体。 【化2】 式中、R1:水素、メチル基 R2,R3,R4,R5:水素、同一もしくは相異なって、
置換、未置換の直鎖又は分岐のアルキル基又はアルコキ
シ基、置換、未置換のアリール基、アリールオキシ基、
アラルキルオキシ基、ハロゲン、置換、未置換のアミノ
1 :1〜10の整数 2 :1〜4の整数 3 ,n 4 :1〜5の整数 m,k:0又は1 【化3】 式中、R1:水素、メチル基 R6:直鎖又は分岐の炭素数1〜20のアルキル基、置
換、未置換のアリール基、アラルキル基 【化4】 式中、R1:水素、メチル基 5 :1〜10の整数
5. An electrophotographic photoreceptor in which a charge generation layer and a charge transfer layer are sequentially laminated on a conductive support, wherein the charge transfer layer contains a repeating unit represented by the following formula (2) and a compound represented by the following formula (3).
And a repeating unit represented by the following chemical formula 4, and a repeating unit represented by the following chemical formula 2
2. The product represented by the formula (1) according to claim 1, which gives a unit.
30 to 90% by weight of the mer
20 to 40% by weight of a monomer giving a unit,
A monomer which gives a repeating unit represented by the formula:
An electrophotographic photoreceptor comprising an isocyanate cured product of an acryl or methacrylic ester copolymer (III) obtained by polymerizing a monomer mixture containing 1% by weight . Embedded image In the formula, R 1 : hydrogen, methyl group R 2 , R 3 , R 4 , R 5 : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n 1 : integer of 10 to 10 n 2 : integer of 1 to 4 n 3 , n 4 : integer of 1 to 5 m, k: 0 or 1 ] In the formula, R 1 : hydrogen, methyl group R 6 : linear or branched alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group, aralkyl group In the formula, R 1 : hydrogen, methyl group n 5 : an integer of 1 to 10
JP17381792A 1991-07-12 1992-06-08 Acrylic or methacrylic acid ester having novel triphenylamine skeleton, novel polymer obtained therefrom, and electrophotographic photoreceptor using the polymer Expired - Lifetime JP3164426B2 (en)

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