JPH04174852A - Electrophotographic sensitive material - Google Patents
Electrophotographic sensitive materialInfo
- Publication number
- JPH04174852A JPH04174852A JP30361990A JP30361990A JPH04174852A JP H04174852 A JPH04174852 A JP H04174852A JP 30361990 A JP30361990 A JP 30361990A JP 30361990 A JP30361990 A JP 30361990A JP H04174852 A JPH04174852 A JP H04174852A
- Authority
- JP
- Japan
- Prior art keywords
- electric charge
- charge generating
- charge generation
- charge
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000012546 transfer Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 28
- 108091008695 photoreceptors Proteins 0.000 claims description 18
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 15
- -1 perylene compound Chemical class 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 125000005577 anthracene group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 230000027455 binding Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- RZRJYURCNBXIST-UHFFFAOYSA-N 2-anthroic acid Chemical compound C1=CC=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 RZRJYURCNBXIST-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-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
- 229910016523 CuKa Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、帯電−露光−現像等のプロセスをとる電子
写真用感光体に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to an electrophotographic photoreceptor that undergoes processes such as charging, exposure, and development.
従来の技術
従来、電子写真用感光体としては、感光材料に無機光導
電性物質を用いるものと、有機光導電性物質を用いるも
のとが如られている。前者の無機光導電性物質には、セ
レン、酸化亜鉛、酸化チタン、硫化カドミウムなどがあ
り、後者の有機光導電性物質には、フタロシアニン顔料
、ジスアゾ系顔料などがある。2. Description of the Related Art Conventionally, electrophotographic photoreceptors include those using inorganic photoconductive materials and those using organic photoconductive materials as photosensitive materials. The former inorganic photoconductive substances include selenium, zinc oxide, titanium oxide, and cadmium sulfide, and the latter organic photoconductive substances include phthalocyanine pigments and disazo pigments.
前者の無機光導電性物質を用いた感光体は、熱安定性、
耐久性等の点が十分とは言えなかったり、あるいは、無
機光導電性物質に毒性があって製造上や取扱上で問題が
あったりという不都合がある。The former photoreceptor using an inorganic photoconductive material has thermal stability,
There are disadvantages in that durability and the like are not sufficient, or the inorganic photoconductive substance is toxic, causing problems in manufacturing and handling.
一方、後者の有機光導電性物質を用いた感光体(以下、
適宜[○PCJと言う)は、無公害で生産性や経済性に
優れ、有機光導電性物質は分子設計による感光特性の調
整も可能であるなどの特徴があることから、開発が進め
られ実用化されており、現在では、電子写真用感光体の
主力になりつつある。On the other hand, the latter photoreceptor (hereinafter referred to as
Due to its features such as non-polluting, excellent productivity and economy, and the ability to adjust the photosensitive characteristics of organic photoconductive materials through molecular design, it has been developed and put into practical use. It is now becoming the mainstay of electrophotographic photoreceptors.
OPCは、通常、光を吸収してキヤ】ファを発生させる
電荷発生層(CG層)と生成したキャリアを移動させる
電荷移動層(CT層)の2重層構造で使用され、その高
感度化が図られている。一般に、2重層構造では高感度
化のためにCG層は数μmの厚さで形成され、CT層は
数十μmの厚さで形成される。このとき、強度、耐刷性
等の理由から、CG層は基体側に形成され、CT層は表
面側に形成されるのが普通である。そして、CT剤(電
荷移動剤)としては正孔の移動により作動するものしか
実用化されておらず、したがって、その電子写真用感光
体は必然的に負帯電方式となる。OPC is usually used with a double layer structure consisting of a charge generation layer (CG layer) that absorbs light and generates carriers and a charge transfer layer (CT layer) that moves the generated carriers. It is planned. Generally, in a double layer structure, the CG layer is formed to have a thickness of several μm, and the CT layer is formed to have a thickness of several tens of μm, in order to increase sensitivity. At this time, for reasons such as strength and printing durability, the CG layer is usually formed on the base side and the CT layer is formed on the surface side. As CT agents (charge transfer agents), only those that operate by the movement of holes have been put to practical use, and therefore, the electrophotographic photoreceptor is necessarily of a negative charging type.
発明が解決しようとする課題
しかしながら、従来の負帯電方式の感光体には、■帯電
に用いられる負電荷により空気中の酸素がオゾンになる
(このオゾンは人体に有害なだけでなく、しばしば感光
体の酸化を引き起こし感光体の劣化を促進する) ■帯
電が不完全である■ドラム表面の影響を受けやすい、と
いう問題がある。Problems to be Solved by the Invention However, with conventional negatively charged photoreceptors, the negative charge used for charging converts oxygen in the air into ozone (this ozone is not only harmful to the human body, but also often (causing oxidation of the body and accelerating deterioration of the photoreceptor) ■Charging is incomplete ■Easy to be affected by the drum surface.
以上の事情に鑑み、この発明は、従来のOPCのもつ上
記欠点を解消し、高性能で耐久性に優れた電子写真用感
光体を提供することを目的とする。In view of the above circumstances, it is an object of the present invention to eliminate the above-mentioned drawbacks of conventional OPCs and to provide an electrophotographic photoreceptor with high performance and excellent durability.
課題を解決するだめの手段
発明者らは、上記目的を達成するため、様々な角度から
OPCの検討を行い、電荷発生層と電荷移動層のうちの
電荷発生層のバインダー用高分子化合物に注目し鋭意検
討を加え、下記式の構造を有する高分子化合物が上記課
題の解決に適したものであることを見出し、先に提案し
た(特願平2−135915)。Means to Solve the Problem In order to achieve the above object, the inventors investigated OPC from various angles and focused on a polymer compound for the binder of the charge generation layer of the charge generation layer and the charge transfer layer. After extensive research, it was discovered that a polymer compound having the structure of the following formula is suitable for solving the above problems, and was previously proposed (Japanese Patent Application No. 2-135915).
(但し、Xl、X2:少なくとも一方がBrであること
、すなわち、少な(とも一方のベンゼン環の水素の内に
Brで置換(100%置換も含む)されたものがあるこ
と)
そして、より優れた実用性の高いものとするために、さ
らに検討を続け、上記高分子化合物と共に芳香族カルボ
ン酸を併用することが、非常に効果的であることを見出
し、この発明を完成させることができた。(However, Xl, X2: At least one of them must be Br, that is, there must be a small number of hydrogens in the benzene ring of both of them substituted with Br (including 100% substitution)). In order to make it more practical, we continued to study and found that the combination of aromatic carboxylic acid with the above-mentioned polymer compound was very effective, and we were able to complete this invention. .
したがって、この発明にかかる電子写真用感光体では、
電荷発生層と電荷移動層が重ね合わされてなり、前記電
荷発生層が、上記式であらわされる構造を有するバイン
ダー用高分子化合物および芳香族カルボン酸を含み電荷
発生剤が分散されている混合物の熱硬化膜である構成を
とるようにしている。Therefore, in the electrophotographic photoreceptor according to the present invention,
Heat generation of a mixture in which a charge generation layer and a charge transfer layer are superimposed, and the charge generation layer contains a binder polymer compound having a structure represented by the above formula and an aromatic carboxylic acid, and a charge generation agent is dispersed therein. The structure is made of a cured film.
この発明で用いられる芳香族カルボン酸には、例えば、
請求項2のように、ベンゼン環、ナフタレン環、アント
ラセン環およびフェナントレン環のうちの少なくとも一
つの芳香環を有する化合物が挙げられる。芳香族カルボ
ン酸の添加量は、普通、上記バインダー用高分子化合物
(樹脂材)100wt%に対し2〜30Wt1程度であ
る。添加量が多過ぎると感度が悪くなるという不都合が
ある。The aromatic carboxylic acids used in this invention include, for example,
As claimed in claim 2, examples thereof include compounds having at least one aromatic ring selected from a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. The amount of aromatic carboxylic acid added is usually about 2 to 30 Wt1 per 100 wt% of the above-mentioned binder polymer compound (resin material). If the amount added is too large, there is a disadvantage that sensitivity deteriorates.
この発明において電荷発生剤としては、後述するX型フ
タロシアニンが適切なものとして挙げられるが、この場
合、請求項3のように、混合物中に電荷発生剤用粒子状
X型フタロシアニンと共に分子状フタロシアニンが含ま
れている形態が好ましい。In this invention, X-type phthalocyanine, which will be described later, is suitable as the charge-generating agent. In this case, as in claim 3, molecular phthalocyanine is included in the mixture together with the particulate X-type phthalocyanine for the charge-generating agent. A form in which it is included is preferred.
この他の電荷発生剤としては、請求項4のように、ペリ
レン系化合物、フタロシアニン系化合物、チアピリリウ
ム系化合物、スクアリリウム系化合物、ビスアゾ系化合
物、トリスアゾ系顔料、アズレニウム系色素が挙げられ
る。これらの電荷発生剤の利用形態は、単独使用に限ら
ず、複数併用の形態もある。Other charge generating agents include perylene compounds, phthalocyanine compounds, thiapyrylium compounds, squarylium compounds, bisazo compounds, trisazo pigments, and azulenium dyes. These charge generating agents are not limited to being used alone, but may also be used in combination.
電荷発生剤とバインダー用高分子化合物の重量比は、通
常、1:1〜1:10程度の間にある。電荷発生剤の方
が前記比率(1: l)を越えて多くなると感光特性は
上がっても帯電特性が劣化し500■以上の電位を乗せ
ることが難しくなる。逆にバインダー用高分子化合物の
方が前記比率(1:10)を越えて多くなると十分な感
光特性をもたせることが難しくなる。The weight ratio of the charge generating agent to the binder polymer is usually between about 1:1 and 1:10. If the amount of the charge generating agent exceeds the above ratio (1:l), the photosensitive characteristics will improve, but the charging characteristics will deteriorate, making it difficult to apply a potential of 500 .mu.m or more. On the other hand, if the amount of the binder polymer compound exceeds the above ratio (1:10), it becomes difficult to provide sufficient photosensitivity.
通常、バインダー用高分子化合物に対し溶剤も用いて混
合物を作る。適当な溶剤としては、ニトロベンゼン、ク
ロルベンゼン、ジクロルベンゼン、ジクロルメタン、ト
リクロルエチレン、クロルナフタレン、メチルナフタレ
ン、ベンゼン、トルエン、キシレン、テトラヒドロフラ
ン、シクロヘキサノン、1.4−ジオキサン、Nメチル
ピロリドン、四塩化炭素、ブロムブタン、エチレングリ
コール、スルホラン、エチレンクリコールブチルエーテ
ル、アセトキシエトキシエタン、ピリジン等が挙げられ
る。Usually, a mixture is prepared by also using a solvent for the polymer compound for the binder. Suitable solvents include nitrobenzene, chlorobenzene, dichlorobenzene, dichloromethane, trichloroethylene, chlornaphthalene, methylnaphthalene, benzene, toluene, xylene, tetrahydrofuran, cyclohexanone, 1,4-dioxane, N-methylpyrrolidone, carbon tetrachloride, Examples include bromobutane, ethylene glycol, sulfolane, ethylene glycol butyl ether, acetoxyethoxyethane, and pyridine.
このように、バインダー用高分子化合物、芳香族カルボ
ン酸、電荷発生剤、溶剤等を用いて作られた混合物を、
パーコーター、カレンダーコーター、スピンコーター、
ブレードコーター、デイツプコーターグラビアコーター
等を使用し、基板(ドラムやベルト等)表面に塗布して
熱処理し硬化させる。得られた熱硬化膜が電荷発生層で
ある。In this way, a mixture made using a binder polymer compound, an aromatic carboxylic acid, a charge generating agent, a solvent, etc.
percoater, calendar coater, spin coater,
Using a blade coater, dip coater, gravure coater, etc., it is applied to the surface of a substrate (drum, belt, etc.) and cured by heat treatment. The resulting thermoset film is a charge generation layer.
熱処理条件は、普通、温度:100〜200℃程度、処
理時間:30〜120分程度である。The heat treatment conditions are usually a temperature of about 100 to 200°C and a treatment time of about 30 to 120 minutes.
続いて、電荷発生層の上へ電荷移動層を形成する。電荷
移動剤、バインダー用高分子化合物および溶剤等からな
る混合物を塗布し熱処理し電荷移動層とする。この発明
のOPCの電荷発生層たる熱硬化膜は耐溶剤性に優れる
ため、電荷移動層の形成に使われる溶剤の種類に制限が
少ないという利点がある。また、電荷移動層の上に絶縁
性保護膜を形成してもよい。Subsequently, a charge transport layer is formed on the charge generation layer. A mixture consisting of a charge transfer agent, a binder polymer compound, a solvent, etc. is applied and heat treated to form a charge transfer layer. Since the thermosetting film serving as the charge generation layer of the OPC of the present invention has excellent solvent resistance, there is an advantage that there are few restrictions on the type of solvent used to form the charge transfer layer. Further, an insulating protective film may be formed on the charge transfer layer.
電荷移動剤としては、一般に知られているもの、例えば
、ヒドラゾン化合物、オキサゾール化合物、トリフェニ
ルメタン化合物、アリールアミン化合物などが挙げられ
る。Examples of the charge transfer agent include commonly known ones, such as hydrazone compounds, oxazole compounds, triphenylmethane compounds, and arylamine compounds.
電荷移動層用バインダー用高分子化合物や保護膜用高分
子化合物としては、前記式であらわされるものの他、ポ
リエステル、ポリカーボネイト、ポリメタクリレート、
ポリスチレン、ポリエーテル、ポリビニル系化合物、あ
るいは、これらの共重合体、ブレンド物等が電荷発生層
に対し良好な接合性を示すので好ましい。溶剤も前述の
ものを用いることができる。In addition to those represented by the above formula, examples of the polymer compound for the binder for the charge transfer layer and the polymer compound for the protective film include polyester, polycarbonate, polymethacrylate,
Polystyrene, polyether, polyvinyl compounds, or copolymers and blends thereof are preferred since they exhibit good bonding properties to the charge generation layer. The solvents mentioned above can also be used.
電荷発生層は熱硬化膜であるため、電荷移動層をその上
に形成する際に、電荷発生層と同じ(上記式で示す構造
の)バインダー用高分子化合物、芳香族カルボン酸およ
び溶剤を用いることも可能である。この場合、電荷発生
層と電荷移動層の接合状態が極めて良好で安定し感光特
性は向上し、機械的強度も増し耐刷性が向上するととも
に、絶縁層保護膜も積層する場合も、保護膜形成に使う
溶剤の制限も少ない。Since the charge generation layer is a thermosetting film, when forming the charge transfer layer thereon, the same binder polymer compound (having the structure shown in the above formula), aromatic carboxylic acid, and solvent as the charge generation layer are used. It is also possible. In this case, the bonding state between the charge generation layer and the charge transfer layer is extremely good and stable, the photosensitivity is improved, the mechanical strength is increased, and the printing durability is improved. There are also fewer restrictions on the solvents used for formation.
作用
この発明の電子写真用感光体の電荷発生層は、前記式で
示すバインダー用高分子化合物を用いているため、堅く
て緻密な耐熱性の良い膜質であるが、芳香族カルボン酸
が併用され熱処理されていると、この膜質傾向がより強
められる。すなわち、より耐久性に富む(例えば、耐オ
ゾン性に優れる)膜質になるのである。Function The charge generation layer of the electrophotographic photoreceptor of the present invention uses the binder polymer compound represented by the above formula, so it is a hard, dense film with good heat resistance. If heat treated, this film quality tendency will be further strengthened. In other words, the film becomes more durable (for example, has excellent ozone resistance).
前記バインダー用高分子化合物は各種電荷発生剤および
溶剤に対して相溶性が良(十分な量を分散させても良質
で均一な膜となるため、高性能化が図れる。The binder polymer compound has good compatibility with various charge generating agents and solvents (even when dispersed in a sufficient amount, a good quality and uniform film is formed, so high performance can be achieved).
実施例
以下、この発明の電子写真用感光体の実施例を説明する
。なお、この発明は下記の実施例に限らないことは言う
までもない。Examples Examples of the electrophotographic photoreceptor of the present invention will be described below. It goes without saying that this invention is not limited to the following embodiments.
この発明のOPCにおいて、電荷発生のためにX型フタ
ロシアニンを用いる場合、同X型フタロシアニンは上記
バインダー用高分子化合物と相溶性が良く適切であるこ
とは発明者らが見出したことであるので、以下に具体的
に説明しておく。In the OPC of this invention, when X-type phthalocyanine is used for charge generation, the inventors have found that the X-type phthalocyanine has good compatibility with the binder polymer compound and is suitable. This will be explained in detail below.
フタロシアニンには、中心に金属原子を有する金属フタ
ロシアニンと、金属原子を有しない無金属フタロシアニ
ンがある。後者の無金属フタロシアニン(以下、Ht−
pcと略す)には、従来、α型とβ型の2種類が、その
代表として知られていた。Phthalocyanines include metal phthalocyanines that have a metal atom in the center and metal-free phthalocyanines that do not have a metal atom. The latter metal-free phthalocyanine (hereinafter referred to as Ht-
(abbreviated as pc), two types, α type and β type, have been known as representative types.
これに対して、近時、ゼロックス(Xerox)社が優
れた電子写真特性を有するX型nt−pcを開発し、そ
の合成法、結晶型と電子写真特性との関係、構造解析な
どの研究を行っている(USP3. 357゜989)
。X型)(t −Pcは、常法により合成したβ型Hz
−Pcを硫酸処理によりα型とし、これを長時間ポール
ミリングすることにより作製する。その結晶構造は、従
来のα型およびβ型と明らかに異なっている。X型H,
−PCのX線回折図(CuKa線による測定)によれば
、その回折線は、2θ=7.4゜9.0. 15.1.
16.5. 17.2. 20.1. 20.6.
20.7゜21.4. 22.2. 23.8. 27
.2. 28.5. 30.3(単位0)に出現する。In response to this, Xerox has recently developed X-type NT-PC, which has excellent electrophotographic properties, and is conducting research on its synthesis method, the relationship between crystal type and electrophotographic properties, and structural analysis. (USP 3.357°989)
. X type) (t-Pc is β type Hz synthesized by a conventional method
-Pc is made into the α form by sulfuric acid treatment, and this is produced by pole milling for a long time. Its crystal structure is clearly different from the conventional α and β forms. X type H,
- According to the X-ray diffraction diagram (measured using CuKa radiation) of PC, its diffraction lines are 2θ=7.4°9.0. 15.1.
16.5. 17.2. 20.1. 20.6.
20.7°21.4. 22.2. 23.8. 27
.. 2. 28.5. Appears in 30.3 (unit 0).
もっとも強度の高い回折線は、7.5゜(面間隔d=1
1.8′Aに相当)付近の回折線であって、その強度を
1とすると、9.1°付近の回折線強度(面間隔d=9
.8Aに相当)は066である。The most intense diffraction line is 7.5° (planar spacing d=1
If the intensity of the diffraction line near 9.1° (corresponding to 1.8'A) is 1, then the intensity of the diffraction line near 9.1° (corresponding to d=9
.. 8A) is 066.
X型H2−PCバインダー用高分子化合物と共に溶媒に
添加し撹拌混合(混練)して分散させる。It is added to a solvent together with the polymer compound for the X-type H2-PC binder and dispersed by stirring and mixing (kneading).
撹拌混合を十分に行うとX型Ht−pcは微粒子化され
ると同時に一部が可溶化する(粘度が上昇していること
から可溶化していると考えられる)。混合物中には電荷
発生剤用粒子状X型nz−E’cとは違う分子状のHl
−PCを生じたものと考えられる。When stirring and mixing are performed sufficiently, the X-type Ht-pc is turned into fine particles and at the same time partially solubilized (it is considered that the viscosity is increased, so it is solubilized). The mixture contains Hl in a molecular form different from the particulate X-type nz-E'c for the charge generating agent.
- It is thought that this caused PC.
そして、分子状の)(z −Pcの存在がCT機能をも
たらしているものと推察している。X型Ht−pcを用
いた場合、X線回折図は、X型)Jt−Pc単独の回折
図とは明らかに異なっており、また、α型およびβ型の
)(t −Pcの回折図とも明らかに異なり、すなわち
、そのX線回折図は、X型)(、−Pc0X線回折図に
比べ、2θ−214°以上の回折線が消失する傾向にあ
り、16.5°付近の回折線は増加する傾向にある。最
も顕著な変化は、Ha −Pcの最も特徴的な回折線す
なわち75°(d == 11.8A)付近および91
°(d−98人)付近の2本の回折線のうち、75°付
近の回折線のみが選択的に消失していることである。こ
のことから、X型H,−Pcの少なくとも一部が新しい
ものに変化したと推察されるのである。It is inferred that the presence of molecular (z-Pc) provides the CT function. When X-type Ht-pc is used, the X-ray diffraction pattern is similar to that of X-type) Jt-Pc alone. It is clearly different from the diffractogram of α- and β-forms)(t-Pc, i.e., its X-ray diffraction pattern is different from the X-ray diffractogram of Compared to Around 75° (d == 11.8A) and 91
Of the two diffraction lines near 75° (d-98 people), only the diffraction line near 75° has selectively disappeared. From this, it is inferred that at least a part of the X-type H, -Pc has changed into a new one.
撹拌混合の程度(通常は1日以上の撹拌が必要)時間、
温度などは用いられる溶剤等によって異なる。適切な処
理の程度は、先に述べたX#!回折パターンの7.5°
付近、91°付近の回折線強度比(1,、、、/1.、
=)で見ることができる。この比が1〜01の間にある
ようにすることが好ましい。Degree of stirring and mixing (usually one day or more of stirring is required) time,
Temperature etc. vary depending on the solvent used. The appropriate degree of processing is X#! 7.5° of diffraction pattern
Diffraction line intensity ratio near 91° (1, , , /1.,
=) can be seen. Preferably, this ratio is between 1 and 01.
上記のように、X型無金属フタロシアニン、バインダー
用高分子化合物、芳香族カルボン酸、溶剤を一緒にして
、ボールミル、アトライター、サンドミル、サンドグラ
ンドなどを用いた方法で混合した後、塗布・熱処理し熱
硬化膜化する。As mentioned above, the X-type metal-free phthalocyanine, binder polymer, aromatic carboxylic acid, and solvent are mixed together using a ball mill, attritor, sand mill, sand gland, etc., and then coated and heat-treated. and heat cured film.
混合処理中に7タロシアニンは、処理が進ムにつれ、一
部が可溶化すると同時に微粒子化され、適切に分散され
た状態となり、さらには粘度が上昇し、形成される膜の
光吸収率もよくなる。膜の光吸収率が良くなる原因は詳
らかではないが、混合処理の間に可溶化したX型フタロ
シアニンとノくインダー用高分子化合物の間で相互作用
が起こるからであろうと推察している。During the mixing process, as the process progresses, part of the 7-talocyanine becomes solubilized and at the same time becomes finely dispersed, becoming properly dispersed, further increasing its viscosity and improving the light absorption rate of the formed film. . The reason why the light absorption rate of the film improves is not clear, but it is surmised that it is due to the interaction between the X-type phthalocyanine solubilized during the mixing process and the polymeric compound for the binder.
この発明のOPCの電荷発生層において、X型フタロシ
アニンが用いられた場合、下記のような特徴を有するこ
とになる。When X-type phthalocyanine is used in the charge generation layer of the OPC of this invention, it will have the following characteristics.
■ 非常に高感度である。2 lux −secに達す
るものもある。■ Extremely sensitive. Some reach 2 lux-sec.
■ 550〜800 nmの広い波長範囲で感度がよい
という優れた感光特性を有する。(2) It has excellent photosensitivity, being sensitive over a wide wavelength range of 550 to 800 nm.
なお、上記XmH,−PC以外の結晶型をもつH,−P
Cとして、τ型’H,−Pcがある。これは、α、β、
X型結晶を摩砕助剤とともに不活性溶剤中5〜10℃、
20時間ボールミリングすることによって得られる。そ
のXls回折パターンは本質的にX型のそれに類似して
いる。ただし、この場合は、7.5°付近の回折強度と
9.1°付近の回折線強度の比率は1:08になってい
る。このτ型H1−PCもX型Ht−Pcと同様に用い
ることが可能である。In addition, H, -P having a crystal type other than the above XmH, -PC
As C, there is a τ type 'H, -Pc. This is α, β,
Type X crystals are mixed with a grinding aid in an inert solvent at 5-10°C.
Obtained by ball milling for 20 hours. Its Xls diffraction pattern is essentially similar to that of type X. However, in this case, the ratio of the diffraction line intensity around 7.5° to the diffraction line intensity around 9.1° is 1:08. This τ type H1-PC can also be used in the same way as the X type Ht-Pc.
この発明の電子写真用感光体は、例えば、複写機、プリ
ンター、ファクシミリなどの記録用機器に使われるが、
これ以外の用途に用いられてもよい。The electrophotographic photoreceptor of the present invention is used, for example, in recording equipment such as copying machines, printers, and facsimile machines.
It may also be used for other purposes.
この発明は、上記構成に限らない。電荷移動層の上に電
荷発生層がくる構成であっても同様の効果を得ることが
できる。This invention is not limited to the above configuration. Similar effects can be obtained even with a structure in which the charge generation layer is placed on the charge transfer layer.
以下に更に詳しく述べる。More details are provided below.
実施例I
X型無金属フタロシアニン〔犬日本インキ■製ファスト
ゲンプル−(Fastogen Blue 8120B
) )と、バインダー用高分子化合物としての下記に
示す構造(但しBr化率25チ)を有する高分子化合物
FOC−10(富士薬品製)を1:1の重量比でテトラ
ヒドロフランに溶解し、2−ナフトエ酸をFOC−10
に対し5wt%加え、さらにボールミル法により分散混
合した後、得られた溶液をアルミニウムドラム板表面に
デイツプ法により塗布し、空気中、150℃、2時間の
熱処理を行い硬化させ厚み1μmの電荷発生層を形成し
た。Example I Type X metal-free phthalocyanine [Fastogen Blue 8120B manufactured by Inu Nippon Ink ■
)) and a polymer compound FOC-10 (manufactured by Fuji Yakuhin) having the structure shown below (however, the Br conversion rate is 25 cm) as a polymer compound for binder were dissolved in tetrahydrofuran at a weight ratio of 1:1, and 2 -naphthoic acid FOC-10
After further dispersing and mixing using a ball mill method, the resulting solution was applied to the surface of an aluminum drum plate using a dip method, and heat treated in air at 150°C for 2 hours to harden it and generate a charge with a thickness of 1 μm. formed a layer.
ついで、電荷移動剤としてのヒドラゾン化合物であるC
TC−236(亜南香料製)と、バインダー用高分子化
合物としてのポリエステルをテトラヒドロフランに溶解
混合し、得られた溶液を電荷発生層の上に塗布し熱処理
して厚み15μmの電荷移動層を形成しOPCを得た。Next, C which is a hydrazone compound as a charge transfer agent
TC-236 (manufactured by Anan Koryo Co., Ltd.) and polyester as a binder polymer compound are dissolved and mixed in tetrahydrofuran, and the resulting solution is applied onto the charge generation layer and heat treated to form a charge transfer layer with a thickness of 15 μm. and obtained OPC.
得られたOPCの感光特性等を調べだ。測定には川口電
機■製EPA −81QQ型ペーパーアナライザーを用
い、負帯電状態のOPCにタングステンランプで白色光
を照射するようにして、帯電圧、光感度(半減露光量、
E、/、)、残留電位Vrを測った。また、10000
回の繰り返し試験にかけたものについても同様の測定を
行った。測定結果は第1表の通りである。The photosensitive characteristics of the obtained OPC were investigated. For the measurements, we used an EPA-81QQ paper analyzer manufactured by Kawaguchi Electric, and irradiated the negatively charged OPC with white light from a tungsten lamp to measure the charged voltage, photosensitivity (half-reduced exposure amount,
E,/,) and residual potential Vr were measured. Also, 10000
Similar measurements were made for those that had been subjected to repeated tests. The measurement results are shown in Table 1.
(以 下 余 白)
第1表
実施例2
X型無金属フタロシアニン〔犬日本インキ■製ファスト
ゲンプA、 −(Fastogen Blue 812
OB))と、バインダー用高分子化合物としての下記に
示す構造(但しBr化率50%)を有する高分子化合物
FQC−12(富士薬品製)を1:1の重量比でシクロ
ヘキサノンに溶解し、アントラセン2−カルボン酸を加
え十分に分散混合処理したのち、得られた溶液をアルミ
ニウムドラム板表面にデイツプ法により塗布し、空気中
、150℃、2時間の熱処理を行い厚みl 1mの電荷
発生層を形成した。(Margins below) Table 1 Example 2 X-type metal-free phthalocyanine [Fastogen Blue 812 manufactured by Inu Nippon Ink ■
OB)) and a polymer compound FQC-12 (manufactured by Fuji Pharmaceutical) having the structure shown below (however, the Br conversion rate is 50%) as a polymer compound for binder are dissolved in cyclohexanone at a weight ratio of 1:1, After adding anthracene-2-carboxylic acid and thoroughly dispersing and mixing, the resulting solution was applied to the surface of an aluminum drum plate by the dip method, and heat treated in air at 150°C for 2 hours to form a charge generating layer with a thickness of 1 m. was formed.
ついで、電荷移動剤としてのヒドラゾン化合物であるC
TC〜236(亜南香料製)と、バインダー用高分子化
合物としてのFOC−12をシクロヘキサノンに溶解し
、2−ナフトエ酸を加え十分に混合し、得られた溶液を
電荷発生層の上に塗布し熱処理して厚み15μmの電荷
移動層を形成しOPCを得た。Next, C which is a hydrazone compound as a charge transfer agent
Dissolve TC~236 (manufactured by Anan Koyo Co., Ltd.) and FOC-12 as a polymer compound for binder in cyclohexanone, add 2-naphthoic acid and mix thoroughly, and apply the obtained solution on the charge generation layer. A charge transfer layer having a thickness of 15 μm was formed by heat treatment to obtain an OPC.
得られたOPCについて、繰り返し試験の回数が200
00回である他は、実施例1と同様の測定を行った。測
定結果を第2表に示す。The number of repeated tests for the obtained OPC was 200.
The same measurement as in Example 1 was performed except that the measurement was carried out 00 times. The measurement results are shown in Table 2.
(以 下 余 白)
第2表
さらに温度5〜40℃、湿度20〜85%の範囲にある
様々な雰囲気条件においても上記と同様の測定を行って
みたが、やはり、測定結果には大きな差は出なかった。(Margins below) Table 2 We also carried out measurements similar to the above under various atmospheric conditions ranging from 5 to 40 degrees Celsius and humidity from 20 to 85%, but there were still large differences in the measurement results. It didn't come out.
製造を何回か繰り返し行い、特性が揃ったOPCを再現
性よ(製造できることも確認できた。By repeating the manufacturing process several times, we were able to reproducibly manufacture OPCs with uniform properties.
これらの結果から、実施例のOPCは、帯電圧、光感度
の各特性が極めて優れ、オゾンの発生を伴う負帯電方式
での繰り返し試験の結果が良好であることから、耐オゾ
ン性が向上していることが良(わかる。From these results, the OPC of the example has extremely excellent characteristics such as charging voltage and photosensitivity, and the ozone resistance is improved, as the results of repeated tests using a negative charging method that involve the generation of ozone are good. It's good (I understand).
さらに、実施例2と同様にして複写機(Panas。Furthermore, a copying machine (Panas) was used in the same manner as in Example 2.
n1cNP−1530)、レーザプリンタ(Panas
onicL−136)に取り付けられる形でOPCを作
り、画像等の品7質評価試験を行った。アルミニウムド
ラム用素管の表面粗さ・表面洗浄方法の違う何種類かの
OPCを作り比較したが、OPCの特性に大きな差はあ
られれなかった。この発明のOPCの場合、このように
基材表面の状態が製品の品質に影響せず、歩留まりよく
製造できることも分かった。n1cNP-1530), laser printer (Panas
An OPC was made to be attached to the onic L-136), and a quality evaluation test for images, etc. was conducted. Several types of OPC with different surface roughness and surface cleaning methods were made and compared for raw tubes for aluminum drums, but no major differences were found in the characteristics of the OPC. It has also been found that in the case of the OPC of the present invention, the condition of the base material surface does not affect the quality of the product as described above, and it can be manufactured with a high yield.
A4サイズの試験紙を用いて繰り返しく1万回)印刷を
実行したが、画像流れ、その他の不都合は特にあられれ
なかった。Printing was performed repeatedly (10,000 times) using A4 size test paper, but no image blurring or other problems were observed.
比較例1
実施例1において、2−ナフトエ酸を添加しない他は同
様にしてOPCを得ようとしたが比較例1のOPCは、
2−ナフトエ酸が添加されなかったため、電荷移動層に
用いた、テトラヒドロフランで電荷発生層が溶解し、O
PCを得ることができなかった。Comparative Example 1 An attempt was made to obtain OPC in the same manner as in Example 1 except that 2-naphthoic acid was not added, but the OPC of Comparative Example 1 was
Since 2-naphthoic acid was not added, the charge generation layer was dissolved in tetrahydrofuran, which was used for the charge transfer layer, and O
I couldn't get a PC.
発明の効果
以上に述べたように、この発明にかかる電子写真用感光
体は、電荷発生層に適切な・くインダー作用を有する高
分子化合物と共に芳香族カルボン酸を用いられているた
め、高性能で耐久性に優れた実用性の高いものとなって
いる。Effects of the Invention As described above, the electrophotographic photoreceptor according to the present invention has high performance because aromatic carboxylic acid is used in the charge generation layer together with a polymeric compound having an appropriate binder action. It is highly durable and highly practical.
Claims (4)
前記電荷発生層が、下記式であらわされるバインダー用
高分子化合物および芳香族カルボン酸を含み電荷発生剤
が分散されている混合物の熱硬化膜からなる電子写真用
感光体。 ▲数式、化学式、表等があります▼ (但し、X1、X2:少なくとも一方がBrであること
、すなわち、少なくとも一方のベンゼン環の水素の内に
Brで置換(100%置換も含む)されたものがあるこ
と)(1) A charge generation layer and a charge transfer layer are superimposed,
An electrophotographic photoreceptor, wherein the charge generation layer is a thermosetting film of a mixture containing a binder polymer represented by the following formula and an aromatic carboxylic acid, in which a charge generation agent is dispersed. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X1, X2: At least one of them is Br, that is, at least one of the benzene ring hydrogens is substituted with Br (including 100% substitution) )
、アントラセン環およびフェナントレン環のうちの少な
くとも一つの芳香環を有する請求項1記載の電子写真用
感光体。(2) The electrophotographic photoreceptor according to claim 1, wherein the aromatic carboxylic acid has at least one aromatic ring selected from a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
ニンと共に分子状フタロシアニンも含まれている請求項
1または2記載の電子写真用感光体。(3) The electrophotographic photoreceptor according to claim 1 or 2, wherein the mixture also contains molecular phthalocyanine together with particulate X-type phthalocyanine for charge generation agent.
アニン系化合物、チアピリリウム系化合物、スクアリリ
ウム系化合物、ビスアゾ系化合物、トリスアゾ系顔料、
アズレニウム系色素のうちの少なくとも一つが混合物中
に含まれている請求項1から3までのいずれかに記載の
電子写真用感光体。(4) As a charge generating agent, a perylene compound, a phthalocyanine compound, a thiapyrylium compound, a squarylium compound, a bisazo compound, a trisazo pigment,
The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein at least one of the azulenium dyes is contained in the mixture.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30361990A JPH04174852A (en) | 1990-11-07 | 1990-11-07 | Electrophotographic sensitive material |
DE69101338T DE69101338T2 (en) | 1990-05-25 | 1991-05-24 | Photosensitive materials containing organic photoconductive substances in a polymeric binder comprising aromatic rings linked to OH groups and bromine atoms. |
EP91304740A EP0458651B1 (en) | 1990-05-25 | 1991-05-24 | Photosensitive materials comprising organic photoconductive substances in a binder polymer having aromatic rings, OH groups and bromine joined at the aromatic ring or rings |
US08/045,286 US5304444A (en) | 1990-05-25 | 1993-04-12 | Photosensitive material for electrophotography comprising organic photoconductive substances in a binder polymer having aromatic rings, OH groups and bromine joined at the aromatic ring or rings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30361990A JPH04174852A (en) | 1990-11-07 | 1990-11-07 | Electrophotographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04174852A true JPH04174852A (en) | 1992-06-23 |
Family
ID=17923168
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30361990A Pending JPH04174852A (en) | 1990-05-25 | 1990-11-07 | Electrophotographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04174852A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010110221A1 (en) * | 2009-03-23 | 2010-09-30 | 日産化学工業株式会社 | Polyester composition for forming heat-cured film |
-
1990
- 1990-11-07 JP JP30361990A patent/JPH04174852A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010110221A1 (en) * | 2009-03-23 | 2010-09-30 | 日産化学工業株式会社 | Polyester composition for forming heat-cured film |
CN102361932A (en) * | 2009-03-23 | 2012-02-22 | 日产化学工业株式会社 | Polyester composition for forming heat-cured film |
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