JP2546739B2 - Photoconductive polymer compound - Google Patents
Photoconductive polymer compoundInfo
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- JP2546739B2 JP2546739B2 JP2254723A JP25472390A JP2546739B2 JP 2546739 B2 JP2546739 B2 JP 2546739B2 JP 2254723 A JP2254723 A JP 2254723A JP 25472390 A JP25472390 A JP 25472390A JP 2546739 B2 JP2546739 B2 JP 2546739B2
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は光導電性高分子化合物に関し、更に詳しくは
電子写真感光体や電界発光素子等のキャリヤー輸送物資
に適する光導電性高分子化合物に関する。Description: FIELD OF THE INVENTION The present invention relates to a photoconductive polymer compound, and more particularly, to a photoconductive polymer compound suitable for a carrier transport material such as an electrophotographic photoreceptor and an electroluminescent device. .
［従来の技術］ 従来光導電性化合物としては種々の化合物が用いられ
ており、例えば電子写真感光体においては、無機光導電
性化合物を主成分とする無機感光体が、広く用いられて
きた。しかし、これらは感度、熱安定性、耐湿性、耐久
性等において必ずしも満足し得るものではない。[Prior Art] Conventionally, various compounds have been used as a photoconductive compound. For example, in an electrophotographic photoreceptor, an inorganic photoreceptor containing an inorganic photoconductive compound as a main component has been widely used. However, these are not always satisfactory in sensitivity, thermal stability, moisture resistance, durability and the like.
無機感光体の持つ欠点を克服する目的で様々な有機光
導電性化合物を主成分とする有機感光体の研究・開発が
近年盛んに行われている。In recent years, research and development of organic photoconductors containing various organic photoconductive compounds as main components have been actively conducted in order to overcome the disadvantages of inorganic photoconductors.
このような有機感光体は、焼却が可能であり、無公害
の利点を有し、更に多くのものは塗工により薄膜形成が
可能で大量生産が容易である。それ故にコストが大幅に
低下でき、又、用途に応じて様々な形状に加工する事が
できるという長所を有している。しかしながら、有機感
光体においては、その感度、耐久性に問題が残されてお
り、高感度、高耐久性の有機感光体の出現が強く望まれ
ている。このような点を改良するため、キャリア発生機
能とキャリア輸送機能とを異なる物質にそれぞれ分担さ
せ、より高性能の有機感光体を開発する試みがなされて
いる。このようないわゆる機能分離型の感光体の形態と
しては単層型と積層型の２種類があり、両者とそれぞれ
の材料を広い範囲から選択することができ、任意の性能
を有する感光体を比較的容易に作成し得ることから多く
の研究がなされてきた。このような機能分離型感光体に
おいて、キャリヤー輸送層に用いられるキャリヤー輸送
物質としては、キャリヤー発生層からの電荷の注入効率
が大きく、更にキャリヤー輸送層内で電荷の移動度が大
である化合物を選択する必要がある。そのためには、イ
オン化ポテンシャルが小さい化合物、ラジカルカチオン
が発生しやすい化合物が選ばれるが、中でもトリアリー
ルアミン誘導体（特開昭53-47260号公報）、ヒドラゾン
誘導体（特開昭57-101844号公報）、オキサジアゾール
誘導体（特公昭34-5466号公報）、ヒラゾリン誘導体
（特公昭52-4188号公報）、スチルベン誘導体（特開昭5
8-198043号公報）、トリフェニルメタン誘導体（特公昭
45-555号公報）等の低分子化合物が従来よく用いられて
いる。Such organic photoreceptors can be incinerated and have no pollution, and many of them can be formed into a thin film by coating and are easily mass-produced. Therefore, it has the advantages that the cost can be greatly reduced and that it can be processed into various shapes depending on the application. However, the sensitivity and durability of the organic photoreceptor still have problems, and the appearance of an organic photoreceptor having high sensitivity and high durability has been strongly desired. In order to improve such a point, an attempt has been made to develop a higher performance organic photoreceptor by assigning a carrier generation function and a carrier transport function to different substances, respectively. There are two types of photoconductors of such a so-called function-separated type, a single-layer type and a laminated type. Both types can be selected from a wide range of materials, and photoconductors with arbitrary performance can be compared. Much research has been done because they can be easily created. In such a function-separated type photoreceptor, as the carrier transporting material used in the carrier transporting layer, a compound having a high charge injection efficiency from the carrier generating layer and a large charge mobility in the carrier transporting layer is used. You have to choose. For this purpose, a compound having a low ionization potential and a compound that easily generates a radical cation are selected. Among them, a triarylamine derivative (JP-A-53-47260) and a hydrazone derivative (JP-A-57-101844) Oxadiazole derivatives (JP-B-34-5466), hirazoline derivatives (JP-B-52-4188), and stilbene derivatives (JP-A-5-5188).
No. 8-198043), triphenylmethane derivative
Low molecular weight compounds such as those disclosed in JP-A-45-555) have been conventionally used.
このようなキャリヤー輸送層は多くの場合、ボリカー
ボネート、ポリエステル等の高分子フィルム形成性バイ
ンダー中に分散または溶解された前記の如き低分子化合
物を含む。一般に、輸送層内の高分子フィルム形成性バ
インダーはそれ自体電気的に不活性であり、キャリヤー
輸送物質を含有したときに電気的に活性となる。Such carrier transport layers often comprise a low molecular compound as described above dispersed or dissolved in a polymeric film forming binder such as polycarbonate, polyester, and the like. Generally, the polymeric film-forming binder in the transport layer is itself electrically inactive and becomes electrically active when it contains a carrier transport material.
［発明が解決しようとする課題］ しかしながら、上記の如き低分子化合物の添加はポリ
マー系のガラス転移温度を著しく低下させ、種々の電子
写真プロセスにおける感光層の傷や感光体自体の変形等
機械的強度低下の原因となるのみならず、電荷輸送性能
の向上を目的として低分子化合物の添加量増大をはかっ
た場合、該低分子化合物のポリマー中での結晶化による
析出、相分離等を引きおこし、この結果、更に、感光体
の機械的強度や感度が低下する等の問題を有していた。[Problems to be Solved by the Invention] However, the addition of the low-molecular compound as described above significantly lowers the glass transition temperature of the polymer system, and causes mechanical damage such as damage to the photosensitive layer and deformation of the photosensitive member itself in various electrophotographic processes. Not only does this cause a decrease in strength, but when the amount of the low-molecular compound is increased for the purpose of improving the charge transport performance, precipitation of the low-molecular compound by crystallization in the polymer, phase separation, etc. are caused. As a result, there is a further problem that the mechanical strength and sensitivity of the photoreceptor are reduced.
従って本発明の目的は、結晶析出や相分離をひきおこ
すことなく、優れた機械的強度及び光導電性を感光体等
に付与しうる光導電性高分子化合物を提供することにあ
る。Accordingly, an object of the present invention is to provide a photoconductive polymer compound that can impart excellent mechanical strength and photoconductivity to a photoreceptor or the like without causing crystal precipitation or phase separation.
［課題を解決するための手段］ 本発明者等は前記課題に鑑みて、鋭意研究の結果、本
発明の上記目的は、下記構造単位（Ｉ），（II）及び
（III）の少なくとも１つを含む繰り返し単位を少なく
とも１種有する高分子化合物を提供することにより達成
されることを見出した。[Means for Solving the Problems] In view of the above problems, the present inventors have conducted intensive studies and as a result, have found that the above object of the present invention is at least one of the following structural units (I), (II) and (III) Has been found to be achieved by providing a polymer compound having at least one type of repeating unit containing
［式中、R1，R2，R3，R4及びR5は各々アルキル基又はア
ルコキシ基を表わし、n1及びn3は各々１〜５の整数を、
n2，n4及びn5は各々１〜４の整数を表わす。また、l,m
及びｐはそれぞれ０より大きく、１以下の数を表わ
す。］ 以下に本発明を更に詳細に説明する。 [Wherein, R 1 , R 2 , R 3 , R 4 and R 5 each represent an alkyl group or an alkoxy group, and n 1 and n 3 each represent an integer of 1 to 5,
n 2 , n 4 and n 5 each represent an integer of 1 to 4. Also, l, m
And p each represent a number greater than 0 and 1 or less. Hereinafter, the present invention will be described in more detail.
本発明の高分子化合物は、上記構造単位（Ｉ），（I
I）及び（III）の少なくとも１つを含む繰り返し単位を
少なくとも１種有してなるものであり、単一の繰り返し
単位からなるホモポリマーも、上記構造単位（Ｉ）〜
（III）の少なくとも１つを含み、かつお互いに異なる
二種以上の繰り返し単位からなる共重合体も好ましく本
発明に包含されうる。更に、これらの繰返し単位と他の
重合可能なモノマーとの共重合体も含まれる。これらは
二次元的あるいは三次元網目構造を有するものも含む。The polymer compound of the present invention comprises the above structural units (I) and (I)
It has at least one kind of repeating unit containing at least one of I) and (III), and a homopolymer composed of a single repeating unit also has the above-mentioned structural units (I) to (I).
Copolymers containing at least one of (III) and comprising two or more types of repeating units different from each other can be preferably included in the present invention. Furthermore, copolymers of these repeating units and other polymerizable monomers are also included. These include those having a two-dimensional or three-dimensional network structure.
本発明の高分子化合物としては、構造単位（II）を含
むものが好ましく用いられる。As the polymer compound of the present invention, those containing the structural unit (II) are preferably used.
本発明の高分子化合物中には上記構造単位（Ｉ）〜
（III）の少なくとも一つが50〜100モル％含まれること
が好ましい。In the polymer compound of the present invention, the above structural units (I) to (I)
It is preferable that at least one of (III) is contained in 50 to 100 mol%.
また、本発明の高分子化合物は分子量として、数平均
分子量で3,000〜3,000,000、更に10,000〜1,000,000で
あることが好ましい。Further, the polymer compound of the present invention preferably has a number average molecular weight of 3,000 to 3,000,000, and more preferably 10,000 to 1,000,000, in terms of molecular weight.
本発明において前記構造単位（Ｉ）〜（III）の各々
において、Ｎ原子に結合する三つのフェニル基はいずれ
も置換基R1〜R5のいずれかを有することができる。この
ような置換基としてはメチル基等のアルキル基、メトキ
シ基等のアルコキシ基が挙げられる。また、n1個のR1、
n2個のR2、n3個のR3、n4個のR4及びn5個のR5はそれぞれ
同一での異なっていてもよい。In the present invention, in each of the structural units (I) to (III), any of the three phenyl groups bonded to the N atom can have any of the substituents R 1 to R 5 . Examples of such a substituent include an alkyl group such as a methyl group and an alkoxy group such as a methoxy group. Also, n 1 R 1 ,
n 2 R 2 , n 3 R 3 , n 4 R 4 and n 5 R 5 may be the same or different.
本発明の高分子化合物は更に前述の如く他の重合可能
なモノマーとの共重合体も含むが、このような重合可能
なモノマーとしては、例えばメタクリル酸メチル、メタ
クリル酸エチル、メタクリル酸ブチル等のメタクリル酸
エステルモノマー、アクリル酸メチル、アクリル酸ブチ
ル等のアクリル酸エステルモノマー、スチレン系モノマ
ー、アクリロニトリル等が挙げられる。The polymer compound of the present invention further includes a copolymer with another polymerizable monomer as described above. Examples of such a polymerizable monomer include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Examples include methacrylate monomers, acrylate monomers such as methyl acrylate and butyl acrylate, styrene monomers, and acrylonitrile.
本発明の高分子化合物としては、構造単位（Ｉ）とメ
タクリル酸メチルを好ましくは1:1の割合で含有するも
のが好ましく用いられる。As the polymer compound of the present invention, those containing the structural unit (I) and methyl methacrylate preferably in a ratio of 1: 1 are preferably used.
以下に本発明の高分子化合物の具体例を例示する。 Hereinafter, specific examples of the polymer compound of the present invention will be described.
以下に上記本発明の高分子化合物の合成例を挙げる
が、他の本発明の高分子化合物もこれら合成例に準じて
合成することができる。 The synthesis examples of the polymer compound of the present invention are described below, but other polymer compounds of the present invention can also be synthesized according to these synthesis examples.
合成例1:本発明の高分子化合物（２−１）の合成 ４−ヒドロキシトリフェニルアミン2g（7.7ミリモ
ル）を100ml4つ口フラスコに入れ、脱水したDMF40mlを
加え溶解させた。水素化ナトリウム0.37g（7.7ミリモ
ル）を加え固形物がなくなるまで撹拌した。反応容器を
氷浴上に移し５℃まで冷却し、クロロメチルスチレン1.
18g（7.7ミリモル）を滴下した。５℃で２時間反応させ
た後、室温で一晩反応させた。反応液を200mlのイオン
交換水中に注ぎトルエンで抽出した。トルエン溶液は、
イオン交換水で水層が中性になるまで洗浄した。減圧下
でトルエンを除去し得られた赤褐色オイル状物質をトル
エン／ヘキサン＝2/1混合溶媒に溶解させシリカゲルを
用いて精製した。溶媒を除去して黄色オイル状物質を得
た。（収量2g,収率70％） メチルスチリル４−（N,N−ジフェニルアミノ）−フ
ェニルエーテル11.72g（0.031モル）、メタクリル酸メ
チル3.11g（0.031モル）、AIBN0.31g（0.0019モル）を
重合用アンプルに入れトルエンで50mlとした後、脱気
し、封管した。重合温度60℃、反応時間２時間で重合し
た。重合終了後、直ちに冷水中でアンプルを冷やし、開
封してクロロホルムを加え、20倍量のメタノール中に滴
下した。再沈澱を２度行って目的物を得た。（乾燥重量
3.1g,収率20.9％） 得られたポリマー中におけるトリフェニルアミンの割
合は75重量％であった。また、分子量は１×105であっ
た。Synthesis Example 1: Synthesis of Polymer Compound (2-1) of the Present Invention 2 g (7.7 mmol) of 4-hydroxytriphenylamine was placed in a 100 ml four-necked flask, and 40 ml of dehydrated DMF was added and dissolved. 0.37 g (7.7 mmol) of sodium hydride was added and the mixture was stirred until there was no solid matter. The reaction vessel was transferred to an ice bath, cooled to 5 ° C., and chloromethylstyrene was added.
18 g (7.7 mmol) were added dropwise. After reacting at 5 ° C. for 2 hours, the reaction was carried out at room temperature overnight. The reaction solution was poured into 200 ml of deionized water and extracted with toluene. The toluene solution is
Washing was performed with ion-exchanged water until the aqueous layer became neutral. The reddish brown oily substance obtained by removing toluene under reduced pressure was dissolved in a mixed solvent of toluene / hexane = 2/1 and purified using silica gel. Removal of the solvent gave a yellow oil. (2 g, 70% yield) Polymerization of methylstyryl 4- (N, N-diphenylamino) -phenyl ether 11.72 g (0.031 mol), methyl methacrylate 3.11 g (0.031 mol), AIBN 0.31 g (0.0019 mol) The mixture was placed in an ampoule for use, adjusted to 50 ml with toluene, degassed, and sealed. Polymerization was performed at a polymerization temperature of 60 ° C. and a reaction time of 2 hours. Immediately after the polymerization was completed, the ampoule was cooled in cold water, opened, chloroform was added, and the solution was added dropwise to a 20-fold amount of methanol. Reprecipitation was performed twice to obtain the desired product. (Dry weight
(3.1 g, yield: 20.9%) The proportion of triphenylamine in the obtained polymer was 75% by weight. The molecular weight was 1 × 10 5 .
合成例2:本発明の高分子化合物（３−１）の合成 4,4′−ジヒドロキシトリフェニルアミン10g（0.036
モル）をDMSO300mlに溶解し、水素化ナトリウム（50％
ミリモル）1.9gを添加し、撹拌した。反応容器を５℃ま
で冷却し、クロロメチルスチレン11.95g（0.079モル）
を滴下した。５℃で２時間反応させた後、室温で一晩反
応させた。反応液を200mlのイオン交換水中に注ぎ、オ
イル分をトルエンで抽出した。トルエンを除去して得ら
れた赤褐色オイル成分をトルエン／ヘキサン＝2/1溶媒
を用いて精製し、目的モノマーを得た。（収量12.8g,収
率70％） ビス｛（メチルスチリル）４−（N,N−ジフェニルア
ミノ）｝フェニルエーテル10g（0.02モル）、AIBN0.2g
（0.0012モル）をアンプルに入れトルエンで50mlとした
後、脱気し、封管した。Synthesis Example 2: Synthesis of polymer compound (3-1) of the present invention 10 g of 4,4'-dihydroxytriphenylamine (0.036
Mol) dissolved in 300 ml of DMSO and sodium hydride (50%
(Mmol) was added and stirred. The reaction vessel was cooled to 5 ° C. and chloromethylstyrene 11.95 g (0.079 mol)
Was added dropwise. After reacting at 5 ° C. for 2 hours, the reaction was carried out at room temperature overnight. The reaction solution was poured into 200 ml of deionized water, and the oil was extracted with toluene. The reddish-brown oil component obtained by removing toluene was purified using a toluene / hexane = 2/1 solvent to obtain a target monomer. (Yield 12.8 g, 70% yield) Bis {(methylstyryl) 4- (N, N-diphenylamino)} phenyl ether 10 g (0.02 mol), AIBN 0.2 g
(0.0012 mol) was placed in an ampoule, made up to 50 ml with toluene, degassed, and sealed.
合成例１と同様の方法で重合を行ない目的物を得た。
（収量2.0g,収率20％） 得られたポリマー中におけるトリフェニルアミンの割
合は47.7重量％であり、分子量は２×105であった。Polymerization was carried out in the same manner as in Synthesis Example 1 to obtain the desired product.
(Yield 2.0 g, yield 20%) The ratio of triphenylamine in the obtained polymer was 47.7% by weight, and the molecular weight was 2 × 10 5 .
合成例3:本発明の高分子化合物（５−１）の合成 4,4′,4″−トリヒドロキシトリフェニルアミン5g
（0.017モル）を100ml4つ口フラスコに入れ、脱水したD
MF40mlを加え溶解させた。水素化ナトリウム1.47g（0.0
61モル）を加え撹拌した。反応器を５℃まで冷却し、ク
ロロメチルスチレン9.37g（0.061モル）を滴下し、２時
間反応させたのち室温で一晩反応させた。Synthesis Example 3: Synthesis of polymer compound (5-1) of the present invention 5 g of 4,4 ', 4 "-trihydroxytriphenylamine
(0.017 mol) in a 100 ml four-necked flask
MF (40 ml) was added and dissolved. 1.47 g of sodium hydride (0.0
61 mol) and stirred. The reactor was cooled to 5 ° C., 9.37 g (0.061 mol) of chloromethylstyrene was added dropwise, and the mixture was reacted for 2 hours and then reacted at room temperature overnight.
反応液を200mlのイオン交換水に注ぎトルエンで抽出
した。トルエン溶液を水洗し、トルエンを除去した。オ
イル状物質を精製し、目的モノマーを得た。（収率60
％） 得られたモノマー5g（7.8×10-3モル）とAIBN3.05g
（0.019モル）をトルエン溶液に溶解し、一部を反応さ
せた。得られたポリマー3gをトルエンに溶解し、AIBN0.
92gを加えて、Al電極をもうけたガラス基板上にスピン
コートし、膜を形成した。この膜を加熱し、３次元ポリ
マーを得た。The reaction solution was poured into 200 ml of ion-exchanged water and extracted with toluene. The toluene solution was washed with water to remove toluene. The oily substance was purified to obtain the target monomer. (Yield 60
%) 5 g of the obtained monomer (7.8 × 10 -3 mol) and 3.05 g of AIBN
(0.019 mol) was dissolved in a toluene solution and partially reacted. 3 g of the obtained polymer was dissolved in toluene, and AIBN0.
92 g was added and spin-coated on a glass substrate provided with an Al electrode to form a film. This film was heated to obtain a three-dimensional polymer.
本発明の高分子化合物は、好ましくは電子写真感光
体、電界発光素子等におけるキャリヤー輸送物質として
用いられる。電子写真感光体としては従来公知の種々の
感光体が挙げられ、そのいずれにも適用することができ
る。すなわち、種々の無機又は有機感光体、機能分離型
の単層型又は積層型感光体のいずれにも適用可能であ
る。特に本発明の高分子化合物と組合わせて使用可能な
キャリヤー発生物質としては、例えば電磁波を吸収して
フリーキャリアを発生するものであれば、無機顔料及び
有機顔料の何れも用いることができる。The polymer compound of the present invention is preferably used as a carrier transporting substance in an electrophotographic photoreceptor, an electroluminescent device and the like. As the electrophotographic photoreceptor, various conventionally known photoreceptors can be mentioned, and any of them can be applied. That is, the present invention is applicable to any of various inorganic or organic photoconductors, and a single-layer or stacked-layer photoconductor of a function-separated type. In particular, as the carrier-generating substance that can be used in combination with the polymer compound of the present invention, any of inorganic pigments and organic pigments can be used as long as they can generate free carriers by absorbing electromagnetic waves.
このようなキャリヤー発生物質（CGM）としては以下
のものが例示される。Examples of such a carrier generating substance (CGM) include the following.
（１） 無定型セレン、三方晶系セレン、セレン−砒素
合金、セレン−テルル合金、硫化カドミウム、セレン化
カドミウム、硫セレン化カドミウム、硫化水銀、硫化
鉛、酸化亜鉛、酸化チタン無定型シリコン等の無機顔料 （２） 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、スチルベンアゾ及びチアゾー
ルアゾ顔料等のアゾ系顔料 （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又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） チタニルフタロシアニン、バナジルフタロシア
ニン等の各種金属フタロシアニン、及びα型、β型、γ
型、τ型、τ′型、η型、η′型等の無金属フタロシア
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） ニトロソ系顔料 （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 （15） フルオレノン系顔料 （16） スクアリリウム顔料 （17） アズレニウム化合物 更に、好ましいアゾ化合物、多環キノン系顔料の例に
ついて示す。これら化合物の具体例については特願昭60
-298013号明細書等に詳細に記載されている。(1) Amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium sulfate selenide, mercury sulfide, lead sulfide, zinc oxide, titanium oxide amorphous silicon, etc. Inorganic pigments (2) Azo pigments such as monoazo pigments, polyazo pigments, metal complex azo pigments, pyrazolone azo pigments, stilbene azo and thiazole azo pigments (3) anthraquinone derivatives, anthantrone derivatives, dibenzopyrenequinone derivatives, pyranthrone derivatives, Anthraquinone or polycyclic quinone pigments such as biolanthrone derivatives and isobiolanthrone derivatives (4) Indigo pigments such as indigo derivatives and thioindigo derivatives (5) Various metal phthalocyanines such as titanyl phthalocyanine and vanadyl phthalocyanine; Type, γ
-Type, τ-type, τ'-type, η-type, η'-type and other non-metallic phthalocyanine-based pigments such as phthalocyanine (6) Carbonium-based pigments such as diphenylmethane-based pigments, triphenylmethane pigments, xanthene pigments and acridine pigments (7) Quinone imine pigments such as azine pigments, oxazine pigments and thiazine pigments (8) Methine pigments such as cyanine pigments and azomethine pigments (9) Quinoline pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and naphthoquinone Pigments (13) Naphthalimide pigments (14) Perinone pigments such as bisbenzimidazole derivatives (15) Fluorenone pigments (16) Squarylium pigments (17) Azurenium compounds Further preferred examples of azo compounds and polycyclic quinone pigments It shows about. For specific examples of these compounds, see
-298013 and the like.
（Ｉ−５） Ａ−Ｎ＝Ｎ−Ar1−CH＝CH−Ar2−Ｎ＝Ｎ−Ａ （Ｉ−６） Ａ−Ｎ＝Ｎ−Ar1−CH＝CH−Ar2−CH＝CH−Ar3−Ｎ＝Ｎ
−Ａ （Ｉ−８） Ａ−Ｎ＝Ｎ−Ar1−Ｎ＝Ｎ−Ar2−Ｎ＝Ｎ−Ａ （Ｉ−９） Ａ−Ｎ＝Ｎ−Ar1−Ｎ＝Ｎ−Ar2−Ｎ＝Ｎ−Ar3−Ｎ＝Ｎ
−Ａ ［但し、上記各一般式中、 Ar1，Ar2及びAr3：それぞれ、置換若しくは未置換の
炭素環式芳香族環基、 R1，R2，R3及びR4：それぞれ、電子吸引性基又は水素
原子であって、R1〜R4の少なくとも１つはシアノ基等の
電子吸引性基、 （Ｘは、ヒドロキシ基、 または−NHSO2−R8（但し、R6及びR7はそれぞれ、水素
原子又は置換若しくは未置換のアルキル基、R8は置換若
しくは未置換のアルキル基または置換若しくは未置換の
アリール基）、 Ｙは、水素原子、ハロゲン原子、置換若しくは未置換
のアルキル基、アルコキシ基、カルボキシル基、スルホ
基、置換若しくは未置換のカルバモイル基または置換若
しくは未置換のスルファモイル基（但し、ｍが２以上の
ときは、互いに異なる基であってもよい。）、 Ｚは、置換若しくは未置換の炭素環式芳香族環または
置換若しくは未置換の複素環式芳香族環を構成するに必
要な原子群、 R5は、水素原子、置換若しくは未置換のアミノ基、置
換若しくは未置換のカルバモイル基、カルボキシル基ま
たはそのエステル基、 Ar4は、置換若しくは未置換のアリール基、ｎは、１
または２の整数、 ｍは０〜４の整数である。）］ また、次の一般式［II］群の多環キノン顔料もCGMと
して使用できる。 (I-5) A-N = N-Ar 1 -CH = CH-Ar 2 -N = N-A (I-6) A-N = N-Ar 1 -CH = CH-Ar 2 -CH = CH -Ar 3 -N = N
-A (I-8) A-N = N-Ar 1 -N = N-Ar 2 -N = N-A (I-9) A-N = N-Ar 1 -N = N-Ar 2 -N = N -Ar 3 -N = N
-A [However, in the above general formulas, Ar 1 , Ar 2 and Ar 3 : a substituted or unsubstituted carbocyclic aromatic ring group, respectively, R 1 , R 2 , R 3 and R 4 : an electron withdrawing property A group or a hydrogen atom, wherein at least one of R 1 to R 4 is an electron-withdrawing group such as a cyano group; (X is a hydroxy group, Or —NHSO 2 —R 8 (where R 6 and R 7 are each a hydrogen atom or a substituted or unsubstituted alkyl group, R 8 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group), Y Is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxyl group, a sulfo group, a substituted or unsubstituted carbamoyl group or a substituted or unsubstituted sulfamoyl group (provided that when m is 2 or more, And Z may be different groups from each other.), Z is an atomic group necessary for forming a substituted or unsubstituted carbocyclic aromatic ring or a substituted or unsubstituted heterocyclic aromatic ring, and R 5 is A hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a carboxyl group or its ester group, and Ar 4 is a substituted or unsubstituted aryl group. Group, n is 1
Or an integer of 2, and m is an integer of 0 to 4. )] Further, polycyclic quinone pigments of the following general formula [II] group can also be used as CGM.
一般式［II］： （但し、この一般式中、Ｘ′はハロゲン原子、ニトロ
基、シアノ基、アシル基又はカルボキシル基を表わし、
ｐは０〜４の整数、ｑは０〜６の整数を表わす。） スクアリリウム顔料については特開昭60-258550号公
報等に記載がある。General formula [II]: (However, in this general formula, X ′ represents a halogen atom, a nitro group, a cyano group, an acyl group or a carboxyl group;
p represents an integer of 0 to 4, and q represents an integer of 0 to 6. The squarylium pigment is described in JP-A-60-258550.
チタニルフタロシアニンについては特願昭62-241983
号明細書に記載がある。Japanese Patent Application No. 62-241983 for titanyl phthalocyanine
There is a description in the specification.
アズレニウム化合物については、特願昭62-251188号
明細書に記載がある。The azurenium compound is described in Japanese Patent Application No. 62-251188.
更に、特殊な無金属フタロシアニンについて、特願昭
61-295784号明細書等に記載がある。Furthermore, regarding special metal-free phthalocyanine,
It is described in the specification of 61-295784 and the like.
［実施例］ 以下に、本発明を実施例を挙げて更に具体的に説明す
る。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.
実施例１ 合成例１で合成した本発明の高分子化合物（２−１）
を用いた試料を以下のようにして作製した。Example 1 The polymer compound (2-1) of the present invention synthesized in Synthesis Example 1
Was prepared as follows.
ガラス基板上に、アルミニウム電極を蒸着した。その
上にセレンを蒸着しキャリヤー発生層とした。An aluminum electrode was deposited on a glass substrate. Selenium was deposited thereon to form a carrier generation layer.
本発明の高分子化合物（２−１）0.5gを1,2−ジクロ
ロメタン5mlに溶解した溶液をスピンコーターを用いて
約８μｍの厚みに塗布し、キャリヤー輸送層を形成し
た。A solution prepared by dissolving 0.5 g of the polymer compound (2-1) of the present invention in 5 ml of 1,2-dichloromethane was applied to a thickness of about 8 μm using a spin coater to form a carrier transport layer.
さらにこの上にアルミニウム電極を蒸着し、移動度及
び耐摩耗性測定用の試料とした。Further, an aluminum electrode was vapor-deposited thereon to obtain a sample for measuring mobility and wear resistance.
移動度は通常用いられるTOF方向（タイムオブフライ
ト法）を用いて測定した。The mobility was measured using a commonly used TOF direction (time of flight method).
また、耐摩耗試験はテーバー型摩耗試験機を用い、摩
耗輪CS-10、荷重500gfで測定した。The abrasion resistance test was performed using a Taber-type abrasion tester with a wear wheel CS-10 and a load of 500 gf.
更にキャリヤ輸送層における析出の程度を目視にて評
価した。Further, the degree of precipitation in the carrier transport layer was visually evaluated.
結果を表１に示す。 Table 1 shows the results.
実施例２ 合成例２で合成した本発明の高分子化合物（３−１）
0.2gを1,2−ジクロロエタンに2gに溶解させた溶液を用
いてキャリヤー輸送層を形成した以外は、実施例１と同
様にして、移動度及び耐摩耗性測定用試料を作製し、同
様に評価した。Example 2 Polymer compound of the present invention (3-1) synthesized in Synthesis Example 2
A sample for measuring mobility and abrasion resistance was prepared in the same manner as in Example 1 except that the carrier transport layer was formed using a solution in which 0.2 g was dissolved in 1,2-dichloroethane in 2 g. evaluated.
結果を表１に示す。 Table 1 shows the results.
実施例３ 合成例３で合成した本発明の高分子化合物（５−１）
を用いてキャリヤー輸送層を形成し、試料の上部にSeを
蒸着し、その上にAlを蒸着してキャリヤー発生層とした
以外は実施例１と同様にして移動度及び耐摩耗性測定用
試料を作成し、同様に評価した。結果を表１に示す。Example 3 Polymer compound of the present invention (5-1) synthesized in Synthesis Example 3
, A carrier transport layer was formed, and Se was vapor-deposited on the sample, and Al was vapor-deposited thereon to form a carrier-generating layer. Was prepared and evaluated in the same manner. Table 1 shows the results.
比較例１ トリフェニルアミン0.5g、ダイヤナールBR-80 1g（三
菱レイヨン社製，アクリル樹脂）を1,2−ジクロロエタ
ン10mlに溶解させた溶液をキャリヤー輸送層形成用塗布
液として用い、キャリヤー輸送層を形成した以外は、実
施例１と同様の方法で移動度及び耐摩耗性測定用試料を
作製し、同様に評価した。結果を表１に示す。Comparative Example 1 A solution in which 0.5 g of triphenylamine and 1 g of Dianal BR-80 (manufactured by Mitsubishi Rayon Co., Ltd., acrylic resin) were dissolved in 10 ml of 1,2-dichloroethane was used as a coating solution for forming a carrier transport layer. A sample for measuring the mobility and abrasion resistance was prepared in the same manner as in Example 1 except that was formed, and evaluated in the same manner. Table 1 shows the results.
比較例２ ポリビニルカルバゾール（阿南香料社製ツビコール21
0 0.2gを1,2−ジクロロエタン5mlに溶解させた溶液をキ
ャリヤー輸送層形成用塗布液として用い、キャリヤー輸
送層を形成した以外は、実施例１と同様にして移動度及
び耐摩耗性測定用試料を作製し、同様に評価した。結果
を表１に示す。Comparative Example 2 Polyvinylcarbazole (Tubicol 21 manufactured by Anan Koran Co., Ltd.)
A solution prepared by dissolving 0.2 g in 5 ml of 1,2-dichloroethane as a coating solution for forming a carrier transport layer was used for the measurement of mobility and abrasion resistance in the same manner as in Example 1 except that the carrier transport layer was formed. A sample was prepared and evaluated similarly. Table 1 shows the results.
実施例４ 本発明の高分子化合物（１−１）として分子量が２×
104のものを用いた以外は実施例１と同様にして移動度
及び耐摩耗性測定用試料を作製し、同様に評価した。結
果を表１に示す。Example 4 The polymer compound (1-1) of the present invention has a molecular weight of 2 ×
Except for using 10 4 ones in the same manner as in Example 1 to prepare a mobility and abrasion resistance measurement sample was evaluated in the same manner. Table 1 shows the results.
実施例５ 本発明の高分子化合物（１−１）として分子量が５×
106のものを用いた以外は実施例１と同様にして移動度
及び耐摩耗性測定用試料を作製し、同様に評価した。結
果を表１に示す。Example 5 The polymer compound (1-1) of the present invention has a molecular weight of 5 ×.
Except for using 10 6 intended to produce a mobility and abrasion resistance measurement sample in the same manner as in Example 1, was evaluated in the same manner. Table 1 shows the results.
表１より明らかなように、本発明の高分子化合物を使
用した実施例１〜５はいずれも本発明外のキャリヤー輸
送物質を用いた比較例１及び２のいずれに対しても優れ
た移動度、耐摩耗性及び析出性を有している。 As is clear from Table 1, all of Examples 1 to 5 using the polymer compound of the present invention were superior to Comparative Examples 1 and 2 using a carrier transporting substance outside the present invention in mobility. , Has wear resistance and precipitation properties.
［発明の効果］ 以上詳細に述べたように、本発明の高分子化合物によ
り、結晶析出や相分離をひきおこすことなく、優れた機
械的強度及び光導電性を感光体等に付与することができ
る。[Effects of the Invention] As described in detail above, the polymer compound of the present invention can impart excellent mechanical strength and photoconductivity to a photoreceptor or the like without causing crystal precipitation or phase separation. .
Claims (1)
の少なくとも１つを含む繰り返し単位を少なくとも１種
有する高分子化合物。 ［式中、R1，R2，R3，R4及びR5は各々アルキル基又はア
ルコキシ基を表わし、n1及びn3は各々１〜５の整数を、
n2，n4及びn5は各々１〜４の整数を表わす。また、l,m
及びｐはそれぞれ０より大きく、１以下の数を表わ
す。］1. The following structural units (I), (II) and (III)
A polymer compound having at least one kind of repeating unit containing at least one of the following. [Wherein, R 1 , R 2 , R 3 , R 4 and R 5 each represent an alkyl group or an alkoxy group, and n 1 and n 3 each represent an integer of 1 to 5,
n 2 , n 4 and n 5 each represent an integer of 1 to 4. Also, l, m
And p each represent a number greater than 0 and 1 or less. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2254723A JP2546739B2 (en) | 1990-09-25 | 1990-09-25 | Photoconductive polymer compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2254723A JP2546739B2 (en) | 1990-09-25 | 1990-09-25 | Photoconductive polymer compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04133065A JPH04133065A (en) | 1992-05-07 |
| JP2546739B2 true JP2546739B2 (en) | 1996-10-23 |
Family
ID=17268955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2254723A Expired - Fee Related JP2546739B2 (en) | 1990-09-25 | 1990-09-25 | Photoconductive polymer compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2546739B2 (en) |
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| US8669029B2 (en) | 2011-08-22 | 2014-03-11 | Fuji Xerox Co., Ltd. | Reactive compound, charge transporting film, photoelectric conversion device, electrophotographic photoreceptor and method of producing the same, process cartridge, and image forming apparatus |
| US8846280B2 (en) | 2011-08-22 | 2014-09-30 | Fuji Xerox Co., Ltd. | Compound, charge transporting film, photoelectric conversion device, electrophotographic photoreceptor, process cartridge, and image forming apparatus |
| US8962225B2 (en) | 2012-09-12 | 2015-02-24 | Fuji Xerox Co., Ltd. | Charge transporting film, photoelectric conversion device, electrophotographic photoreceptor, process cartridge, and image forming apparatus |
| US9182687B2 (en) | 2012-09-12 | 2015-11-10 | Fuji Xerox Co., Ltd. | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04133065A (en) | 1992-05-07 |
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