JPH0715591B2 - Multilayer electrophotographic photoconductor - Google Patents
Multilayer electrophotographic photoconductorInfo
- Publication number
- JPH0715591B2 JPH0715591B2 JP6292687A JP6292687A JPH0715591B2 JP H0715591 B2 JPH0715591 B2 JP H0715591B2 JP 6292687 A JP6292687 A JP 6292687A JP 6292687 A JP6292687 A JP 6292687A JP H0715591 B2 JPH0715591 B2 JP H0715591B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- vinylcarbazole
- hydrogen
- layer
- poly
- 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.)
- Expired - Lifetime
Links
- 108091008695 photoreceptors Proteins 0.000 claims description 14
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- JPBGLQJDCUZXEF-UHFFFAOYSA-N chromenylium Chemical class [O+]1=CC=CC2=CC=CC=C21 JPBGLQJDCUZXEF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Chemical group 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- 239000010410 layer Substances 0.000 description 56
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 indium Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- CSMWYVFOQHXFMR-UHFFFAOYSA-M 2-phenylchromenylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=[O+]1 CSMWYVFOQHXFMR-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- YXGWBKCOOBHTPT-UHFFFAOYSA-N benzene;chlorobenzene Chemical compound C1=CC=CC=C1.ClC1=CC=CC=C1 YXGWBKCOOBHTPT-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- GPKUICFDWYEPTK-UHFFFAOYSA-N methoxycyclohexatriene Chemical group COC1=CC=C=C[CH]1 GPKUICFDWYEPTK-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0666—Dyes containing a methine or polymethine group
- G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
- G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、有機光導電性物質を含有する積層型電子写真
感光体に関するものである。TECHNICAL FIELD The present invention relates to a laminated electrophotographic photoreceptor containing an organic photoconductive substance.
従来の技術 従来、電子写真感光体としてセレン、セレン−テルル合
金、硫化カドミウム、酸化亜鉛などの無機光導電性物質
からなる感光体が広く用いられてきた。近年、合成が容
易であり、適当な波長域に光導電性を示す化合物を選択
できるなどの特徴をもつ有機光導電性物質の研究が進め
られている。2. Description of the Related Art Conventionally, as an electrophotographic photosensitive member, a photosensitive member made of an inorganic photoconductive substance such as selenium, selenium-tellurium alloy, cadmium sulfide and zinc oxide has been widely used. In recent years, research on organic photoconductive substances having characteristics such as easy synthesis and selection of a compound exhibiting photoconductivity in an appropriate wavelength range has been advanced.
有機光導電性物質を感光層に用いた電子写真感光体は、
成膜が容易である、可とう性が高く設計の自由度が大き
い、安価で無公害であるなどの長所を有しており、無機
光導電性物質からなる感光体では不可能な電子写真プロ
セス(例えば、ベルト状の感光体を使用)を可能にする
ことができる。その中で、感度及び感光体寿命を改善す
るために、電荷発生層と電荷輸送層とに機能を分離させ
て感光層を形成する積層型電子写真感光体が提案され、
さらに、増感剤の改良、増感方法の開発など活発に研究
が進められている。(例えば、第16回電子写真学会講習
会予稿集) 発明が解決しようとする問題点 しかしながら、前記の有機感光体も、感度、繰り返し安
定性など種々の電子写真感光体としての要求を充分に満
足するには至っていないのが現状である。したがって、
有機光導電性物質の長所をいかし、電子写真感光体とし
て要求される特性を充分に満足する高感度な電子写真感
光体の開発が望まれている。An electrophotographic photoreceptor using an organic photoconductive substance as a photosensitive layer is
The electrophotographic process has advantages such as easy film formation, high flexibility and high degree of freedom in design, inexpensiveness and no pollution, etc., which is not possible with a photoconductor made of an inorganic photoconductive substance. (For example, a belt-shaped photoconductor is used). Among them, in order to improve the sensitivity and the life of the photoconductor, a laminated electrophotographic photoconductor in which a charge generation layer and a charge transport layer are separated in function to form a photoconductive layer, is proposed,
Furthermore, active research is being conducted on the improvement of sensitizers and the development of sensitizing methods. (For example, Proceedings of the 16th Workshop of the Electrophotographic Society) Problems to be Solved by the Invention However, the above-mentioned organic photoconductor also sufficiently satisfies the requirements as various electrophotographic photoconductors such as sensitivity and repeatability. The current situation is that it has not yet been achieved. Therefore,
It is desired to develop a high-sensitivity electrophotographic photosensitive member that fully satisfies the characteristics required for the electrophotographic photosensitive member by taking advantage of the organic photoconductive substance.
問題点を解決するための手段 本発明は、前記問題点に鑑み、下記構造式であらわされ
るトリメチン構造を有するベンゾピリリウム塩を含有す
る電荷発生層と、少なくともポリ−N−ビニルカルバゾ
ールを含有する電荷輸送層との間にブロム化ポリ−N−
ビニルカルバゾールを含有する中間層を設け、順次、導
電性支持体上に積層していることによって高感度でかつ
繰り返し安定性の良い電子写真感光体を提供するもので
ある。Means for Solving the Problems In view of the above problems, the present invention contains a charge generation layer containing a benzopyrylium salt having a trimethine structure represented by the following structural formula, and at least poly-N-vinylcarbazole. Brominated poly-N- with the charge transport layer
By providing an intermediate layer containing vinylcarbazole and sequentially laminating it on a conductive support, an electrophotographic photosensitive member having high sensitivity and good repeated stability is provided.
(式中、R1は水素あるいはフェニル基、R2は水素、P−
メトキシフェニル基、4′−メトキシナフチル1′基あ
るいは2′−メトキシナフチル1′基、R3は水素、メト
キシ基、ニトロ基あるいはフェニル基、R4は水素あるい
はメトキシ基、Xは酸素あるいは硫黄原子をあらわして
いる。) 作用 本発明の積層型電子写真感光体は、電荷発生層と電荷輸
送層との間に中間層を設けたものであり、このようにブ
ロム化−ポリ−N−ビニルカルバゾールを含有する中間
層を設けることによって、感度が向上し、残留電位が減
少するが、この効果について理論的解明はまだ成されて
いない。しかし、積層型感光体では電荷発生層と電荷輸
送層との界面が電子写真特性に大きく影響し、電荷輸送
層中に電荷発生層が溶出すると特性がそこなわれたり、
また両層の界面障壁が大きすぎても充分な特性が得られ
ないため、中間層を設けることによって両層の界面にお
いて注入効率が上がり、このような効果が得られるもの
と思われる。 (In the formula, R1 is hydrogen or a phenyl group, R2 is hydrogen, P-
Methoxyphenyl group, 4'-methoxynaphthyl 1'group or 2'-methoxynaphthyl 1'group, R3 is hydrogen, methoxy group, nitro group or phenyl group, R4 is hydrogen or methoxy group, and X is oxygen or sulfur atom. ing. ) Action The laminated electrophotographic photoreceptor of the present invention has an intermediate layer provided between the charge generation layer and the charge transport layer, and thus an intermediate layer containing brominated-poly-N-vinylcarbazole. Although the sensitivity is improved and the residual potential is decreased by providing, the theoretical elucidation of this effect has not been made yet. However, in the laminated type photoreceptor, the interface between the charge generation layer and the charge transport layer has a great influence on the electrophotographic characteristics, and when the charge generation layer elutes in the charge transport layer, the characteristics are impaired.
Further, if the interfacial barrier between both layers is too large, sufficient characteristics cannot be obtained. Therefore, it is considered that the provision of the intermediate layer improves the injection efficiency at the interface between both layers, and such an effect can be obtained.
実施例 以下、本発明の積層型電子写真感光体について詳細に説
明する。Examples Hereinafter, the laminated electrophotographic photoreceptor of the present invention will be described in detail.
本発明の積層型電子写真感光体の電荷発生層は、トリメ
チン構造を有するベンゾピリリウム塩を、適当なバイン
ダー樹脂を加えて分散又は溶解させ、これを導電性支持
体上に塗布することによって得られる。The charge generating layer of the laminated electrophotographic photoreceptor of the present invention is obtained by dispersing or dissolving a benzopyrylium salt having a trimethine structure by adding a suitable binder resin, and coating the benzopyrylium salt on a conductive support. To be
トリメチン構造を有するベンゾピリリウム塩としては、
具体的には、2−〔3′−3″−フェニル−6″−メト
キシ−2″−ベンゾピラニリデン)プロペニル〕−3−
フェニル−6−メトキシベンゾピリリウムパークロレイ
ト、2−〔3′−3″,6″−ジフェニル−4″−p−メ
トキシフェニル−2″−ベンゾピラニリデン)プロペニ
ル〕−3,6−ジフェニル−4−p−メトキシベンゾピリ
リウムパークロレイト、2−〔3′−(3″−フェニル
−2″−ベンゾピラニリデン)プロペニル〕−3−フェ
ニルベンゾピリリウムパークロレイトなどが挙げられ
る。As the benzopyrylium salt having a trimethine structure,
Specifically, 2- [3′-3 ″ -phenyl-6 ″ -methoxy-2 ″ -benzopyranylidene) propenyl] -3-
Phenyl-6-methoxybenzopyrylium perchlorate, 2- [3'-3 ", 6" -diphenyl-4 "-p-methoxyphenyl-2" -benzopyranylidene) propenyl] -3,6-diphenyl- 4-p-methoxybenzopyrylium perchlorate, 2- [3 ′-(3 ″ -phenyl-2 ″ -benzopyranylidene) propenyl] -3-phenylbenzopyrylium perchlorate and the like can be mentioned.
中間層に用いるブロム化ポリ−N−ビニルカルバゾール
は、ビニルカルバゾール環1個に対して0.5〜2個の臭
素が置換されているもので、ポリ−N−ビニルカルバゾ
ールを、クロルベンゼン−ベンゼンの混合溶剤中で少量
の過酸化ベンゾイルの存在下にて少量のN−ブロムスク
シンイミドにて処理し、加熱後メタノール中に注加する
ことにより容易に合成することができる。The brominated poly-N-vinylcarbazole used for the intermediate layer is one in which 0.5 to 2 bromine atoms are substituted for one vinylcarbazole ring, and poly-N-vinylcarbazole is mixed with chlorobenzene-benzene. It can be easily synthesized by treating with a small amount of N-bromosuccinimide in the presence of a small amount of benzoyl peroxide in a solvent, heating and pouring into methanol.
また、ブロム化ポリ−N−ビニルカルバゾールだけでも
成膜性は有するが、他層との接着性向上、塗布膜の均一
性向上、塗工時の流動性調整などの目的で、必要に応じ
てバインダー樹脂を用いることができる。具体的には、
ポリビニルブチラール、ポリ酢酸ビニル、ポリカーボネ
イト、アクリル樹脂、メタクリル樹脂、またはこれらの
樹脂の共重合体などが挙げられる。また、ブロム化ポリ
−N−ビニルカルバゾールやバインダー樹脂を溶解する
溶剤はブロム化ポリ−N−ビニルカルバゾールによって
限定されるが、具体的には、クロロホルム、塩化メチレ
ン、エ塩化エチレンなどのハロゲン化炭化水素類、クロ
ルベンゼンなどのハロゲン化芳香族類などを用いること
ができる。Although brominated poly-N-vinylcarbazole alone has a film-forming property, it may be used as necessary for the purpose of improving the adhesiveness with other layers, improving the uniformity of the coating film, and adjusting the fluidity during coating. A binder resin can be used. In particular,
Examples thereof include polyvinyl butyral, polyvinyl acetate, polycarbonate, acrylic resin, methacrylic resin, and copolymers of these resins. Further, the solvent for dissolving the brominated poly-N-vinylcarbazole and the binder resin is limited by the brominated poly-N-vinylcarbazole, but specifically, it is halogenated carbonized such as chloroform, methylene chloride, and ethylene chloride. Hydrogen and halogenated aromatics such as chlorobenzene can be used.
このようにして分散、調液された塗布液を通常の塗工液
によって塗布、加熱乾燥し、数μmの膜厚で順次、電荷
発生層、中間層を形成するが、好ましくは0.2〜2μm
の膜厚に形成するのがよい。The coating solution thus dispersed and prepared is applied by a normal coating solution, dried by heating, and a charge generation layer and an intermediate layer are sequentially formed with a film thickness of several μm, preferably 0.2 to 2 μm.
It is preferable to form the film with a thickness of.
電荷輸送層は、前記中間層上に、電荷輸送剤としてポリ
−N−ビニルカルバゾールを溶解した塗液を塗工するこ
とにより得られる。塗液を溶解するための溶剤として
は、トルエン、キシレンなどの芳香族炭化水素類などを
用いることができる。このようにして調液された塗布液
を通常の塗工法によって塗布、加熱乾燥し、数μm〜数
十μmの膜厚で電荷輸送層を形成するが、好ましくは5
〜25μmの膜厚に形成するのがよい。The charge transport layer is obtained by applying a coating liquid in which poly-N-vinylcarbazole is dissolved as a charge transport agent on the intermediate layer. Aromatic hydrocarbons such as toluene and xylene can be used as a solvent for dissolving the coating liquid. The coating solution prepared in this manner is applied by a usual coating method and heated and dried to form a charge transport layer having a film thickness of several μm to several tens of μm, preferably 5 μm.
It is preferable to form the film with a thickness of up to 25 μm.
本発明の積層型電子写真感光体に用いられる導電性支持
体は、従来から知られている導電性を有するものであれ
ばよく、アルミニウム,アルミニウム合金などの金属板
及び金属ドラム、酸化スズ、酸化インジウムなどの金属
酸化物からなる板、またはそれらの金属及び金属酸化物
などを真空蒸着、スパッタリング、ラミネート、塗布な
どによって付着させ導電性処理した各種プラスチックフ
ィルム、紙などである。The conductive support used in the laminated electrophotographic photosensitive member of the present invention may be any one having a conventionally known conductivity, and may be a metal plate such as aluminum or aluminum alloy and a metal drum, tin oxide, or oxide. It is a plate made of a metal oxide such as indium, or various plastic films, paper and the like to which a metal and a metal oxide thereof are attached by vacuum vapor deposition, sputtering, laminating, coating or the like to have been electroconductively treated.
さらに、本発明の積層型電子写真感光体を構成する中間
層及び電荷輸送層には、塗膜の可とう性、均一性、機械
的強度などを向上させるために、o−ターフェニル、エ
ポキシ化合物、フタル酸エステル、マレイン酸エステ
ル、塩素化パラフィンなどの可塑剤を添加してもよい。
また、通常の電子写真感光体と同様に、導電層と電荷発
生層との間にカゼイン、ポリビニルアルコール、ポリビ
ニルブチラールなどの接着層またはバリヤー層を設ける
ことができる。Furthermore, in order to improve the flexibility, uniformity, mechanical strength, etc. of the coating film, the intermediate layer and charge transport layer constituting the laminated electrophotographic photosensitive member of the present invention include o-terphenyl and an epoxy compound. Plasticizers such as phthalates, maleates and chlorinated paraffins may be added.
Further, as in the case of an ordinary electrophotographic photoreceptor, an adhesive layer or a barrier layer of casein, polyvinyl alcohol, polyvinyl butyral or the like can be provided between the conductive layer and the charge generation layer.
このようにして、電荷発生層、中間層、電荷輸送層を導
電性支持体上に積層して形成される本発明の電子写真感
光体は、導電性支持体上に電荷発生層・中間層・電荷輸
送層を順次積層するか、または導電性支持体上に電荷輸
送層・中間層・電荷発生層の準に積層してもよい。前者
の場合は負帯電で感度を有し、後者の場合は正帯電で感
度を有するが、表面膜強度及び耐久性の点から前者の方
が望ましい。Thus, the electrophotographic photosensitive member of the present invention formed by laminating the charge generation layer, the intermediate layer and the charge transport layer on the conductive support has a charge generation layer, an intermediate layer, and an intermediate layer on the conductive support. The charge transport layer may be sequentially laminated, or may be laminated on the conductive support in the order of the charge transport layer, the intermediate layer and the charge generation layer. The former case has negatively charged sensitivity and the latter case has positively charged sensitivity, but the former is preferable from the viewpoint of surface film strength and durability.
以下、具体的に実施例を示すが、本発明は以下の実施例
に示す組合せに限定されるものではない。Examples will be specifically shown below, but the present invention is not limited to the combinations shown in the following examples.
(実施例1) 2−〔3′−(3″,6″−ジフェニル−4″−メトキシ
フェニル−2″ベンゾピラニリデン)プロペニル〕−3,
6−ジフェニル−4−メトキシフェニルベンゾピリリウ
ムパークロレイト1重量部及び塩化ビニル−酢酸ビニル
共重合体(ユニオンカーバイト社製 商品名VMCH)1重
量部を二塩化メチレン100重量部に溶解した。この塗液
をアルミ板上に300rpmにて回転塗布し、80℃にて1時間
乾燥して膜厚0.3μmの電荷発生層を形成した。次に、
ブロム化ポリ−N−ビニルカルバゾール1重量部とO−
ターフェニル0.2重量部をジオキサン50重量部に溶解
し、この塗液を電荷発生層上に200rpmにて回転塗布し、
80℃にて1時間乾燥して膜厚0.5μmの中間層を形成し
た。さらに、ポリ−N−ビニルカルバゾール(亜南香料
株式会社製 商品名ツビコール♯210)1重量部とO−
ターフェニル0.3重量部をトルエン10重量部に溶解し
た。この液を中間層の上にブレード塗布し、80℃にて1
時間乾燥して膜厚15μmの電荷輸送層を形成した。Example 1 2- [3 ′-(3 ″, 6 ″ -diphenyl-4 ″ -methoxyphenyl-2 ″ benzopyranylidene) propenyl] -3,
1 part by weight of 6-diphenyl-4-methoxyphenylbenzopyrylium perchlorate and 1 part by weight of vinyl chloride-vinyl acetate copolymer (trade name VMCH manufactured by Union Carbide Co.) were dissolved in 100 parts by weight of methylene dichloride. This coating solution was spin-coated on an aluminum plate at 300 rpm and dried at 80 ° C. for 1 hour to form a charge generation layer having a thickness of 0.3 μm. next,
1 part by weight of brominated poly-N-vinylcarbazole and O-
0.2 parts by weight of terphenyl was dissolved in 50 parts by weight of dioxane, and this coating liquid was spin-coated at 200 rpm on the charge generation layer,
It was dried at 80 ° C. for 1 hour to form an intermediate layer having a film thickness of 0.5 μm. Furthermore, 1 part by weight of poly-N-vinylcarbazole (trade name Tubicor # 210, manufactured by Anan Fragrance Co., Ltd.) and O-
0.3 parts by weight of terphenyl was dissolved in 10 parts by weight of toluene. This solution is blade-coated on the intermediate layer,
After drying for an hour, a charge transport layer having a film thickness of 15 μm was formed.
このようにして得た積層型電子写真感光体を、静電複写
紙試験装置(株式会社川口電気製作所製EPA-8100)を用
いて、−6kVで帯電した時の表面電位V0(V)、その後
暗所に1秒間放置した時の表面電位V1(V)、5luxの白
色光で露光した時に表面電位が1/2V1(V)まで減衰す
るのに要する露光量E1/2(lux・sec)、及び露光6秒
後の表面電位VR6(V)をそれぞれ測定した。それらの
測定結果を第1表に示す。Using the electrostatic copying paper tester (EPA-8100 manufactured by Kawaguchi Denki Seisakusho Co., Ltd.), the laminated electrophotographic photoreceptor thus obtained was charged at −6 kV to obtain a surface potential V 0 (V), After that, the surface potential V 1 (V) when left in a dark place for 1 second, and the exposure amount E1 / 2 (lux ・ lux) required for the surface potential to decay to 1/2 V 1 (V) when exposed to 5 lux white light sec) and the surface potential VR 6 (V) after 6 seconds of exposure were measured. Table 1 shows the measurement results.
(実施例2) 2−〔3′−(3″,6″−ジフェニル−4″−メトキシ
フェニル−2″−ベンゾピラニリデン)プロペニル〕−
3,6−ジフェニル−4−メトキシフェニルベンゾピリリ
ウムパークロレイトの代りに2−〔3′−(3″−フェ
ニル−2″−ベンゾピラニリデン)プロペニル〕−3−
フェニルベンゾピリリウムパークロレイトを用いた以外
は、実施例1と同様にして感光体の作成及び特性の測定
を行なった。結果を第表に示す。 (Example 2) 2- [3 '-(3 ", 6" -diphenyl-4 "-methoxyphenyl-2" -benzopyranylidene) propenyl]-
2- [3 ′-(3 ″ -phenyl-2 ″ -benzopyranylidene) propenyl] -3-instead of 3,6-diphenyl-4-methoxyphenylbenzopyrylium perchlorate
A photoreceptor was prepared and its characteristics were measured in the same manner as in Example 1 except that phenylbenzopyrylium perchlorate was used. The results are shown in Table 1.
(比較例1) 比較例として、中間層を設けず、電荷発生層、電荷輸送
層のみのサンプルを作成した。(Comparative Example 1) As a comparative example, a sample having only the charge generation layer and the charge transport layer was prepared without providing the intermediate layer.
2−〔3′−〕3″,6″−ジフェニル−4″−メトキシ
フェニル−2″−ベンゾピラニリデン)プロペニル〕−
3,6−ジフェニル−4−メトキシフェニルベンゾピリリ
ウムパークロレイト1重量部と塩化ビニル−酢酸ビニル
共重合体(ユニオンカーバイト社製 商品名VMCH)1重
量部を二塩化メチレン100重量部に溶解した。この塗液
を用いて、実施例1と同様にして電荷発生層を作成し
た。また、電荷輸送層も実施例1と同様にして作成し、
特性の測定を行なった。結果を表に示す。2- [3 '-] 3 ", 6" -diphenyl-4 "-methoxyphenyl-2" -benzopyranylidene) propenyl]-
Dissolve 1 part by weight of 3,6-diphenyl-4-methoxyphenylbenzopyrylium perchlorate and 1 part by weight of vinyl chloride-vinyl acetate copolymer (trade name VMCH manufactured by Union Carbide Co.) in 100 parts by weight of methylene dichloride. did. Using this coating liquid, a charge generation layer was prepared in the same manner as in Example 1. Further, the charge transport layer was also prepared in the same manner as in Example 1,
The characteristics were measured. The results are shown in the table.
(比較例2) 2−〔3′−〕3″,6″−ジフェニル−4″−メトキシ
フェニル−2″−ベンゾピラニリデン)プロペニル〕−
3,6−ジフェニル−4−メトキシフェニルベンゾピリリ
ウムパークロレイトの代りに2−〔3′−(3″−フェ
ニル−2″−ベンゾピラニリデン)プロペニル〕−3−
フェニルベンゾピリリウムパークロレイトを用いた以外
は、比較例1と同様にして感光体の作成及び特性の測定
を行なった。結果を表に示す。(Comparative Example 2) 2- [3 '-] 3 ", 6" -diphenyl-4 "-methoxyphenyl-2" -benzopyranylidene) propenyl]-
2- [3 ′-(3 ″ -phenyl-2 ″ -benzopyranylidene) propenyl] -3-instead of 3,6-diphenyl-4-methoxyphenylbenzopyrylium perchlorate
A photoreceptor was prepared and its characteristics were measured in the same manner as in Comparative Example 1 except that phenylbenzopyrylium perchlorate was used. The results are shown in the table.
発明の効果 以上、本発明の積層型電子写真感光体について詳細に説
明したが、本発明の積層型電子写真感光体は、トリメチ
ン構造を有するベンゾピリリウム塩を含有する電荷発生
層と少なくともポリ−N−ビニルカルバゾールを含有す
る電荷輸送層との間にブロム化ポリ−N−ビニルカルバ
ゾールを含有する中間層を設け、順次、導電性支持体上
に積層して形成することにより、高感度なものとなっ
た。EFFECTS OF THE INVENTION As described above, the laminated electrophotographic photoreceptor of the present invention has been described in detail. The laminated electrophotographic photoreceptor of the present invention includes a charge generation layer containing a benzopyrylium salt having a trimethine structure and at least poly-. An intermediate layer containing brominated poly-N-vinylcarbazole is provided between the charge transporting layer containing N-vinylcarbazole and the layers are sequentially laminated on a conductive support to form a highly sensitive layer. Became.
Claims (2)
を有するベンゾピリリウム塩を含有する電荷発生層と、
少なくともポリ−N−ビニルカルバゾールを含有する電
荷輸送層との間にブロム化ポリ−N−ビニルカルバゾー
ルを含有する中間層を設け、順次、導電性支持体上に積
層していることを特徴とする積層型電子写真感光体。 (式中、R1は水素あるいはフェニル基、R2は水素、p−
メトキシフェニル基、4′−メトキシナフチル1′基あ
るいは2′−メトキシナフチル1′基、R3は水素、メト
キシ基、ニトロ基あるいはフェニル基、R4は水素あるい
はメトキシ基、Xは酸素あるいは硫黄原子をあらわして
いる。)1. A charge generation layer containing a benzopyrylium salt having a trimethine structure represented by the following structural formula:
An intermediate layer containing brominated poly-N-vinylcarbazole is provided between the charge transporting layer containing at least poly-N-vinylcarbazole, and is sequentially laminated on a conductive support. Multilayer electrophotographic photoreceptor. (In the formula, R 1 is hydrogen or a phenyl group, R 2 is hydrogen, p-
Methoxyphenyl group, 4'-methoxynaphthyl 1'group or 2'-methoxynaphthyl 1'group, R 3 is hydrogen, methoxy group, nitro group or phenyl group, R 4 is hydrogen or methoxy group, X is oxygen or sulfur atom Is represented. )
は、カルバゾール環1個に対して、0.5〜2個の臭素が
置換されていることを特徴とする特許請求の範囲第1項
記載の積層型電子写真感光体。2. The laminated type according to claim 1, wherein the brominated poly-N-vinylcarbazole is substituted with 0.5 to 2 bromine atoms per one carbazole ring. Electrophotographic photoreceptor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6292687A JPH0715591B2 (en) | 1987-03-18 | 1987-03-18 | Multilayer electrophotographic photoconductor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6292687A JPH0715591B2 (en) | 1987-03-18 | 1987-03-18 | Multilayer electrophotographic photoconductor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63229460A JPS63229460A (en) | 1988-09-26 |
JPH0715591B2 true JPH0715591B2 (en) | 1995-02-22 |
Family
ID=13214368
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6292687A Expired - Lifetime JPH0715591B2 (en) | 1987-03-18 | 1987-03-18 | Multilayer electrophotographic photoconductor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0715591B2 (en) |
-
1987
- 1987-03-18 JP JP6292687A patent/JPH0715591B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS63229460A (en) | 1988-09-26 |
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