EP0161005A2 - Composés de "squarium", procédé de leur préparation et récepteurs électrophotographiques les contenant - Google Patents
Composés de "squarium", procédé de leur préparation et récepteurs électrophotographiques les contenant Download PDFInfo
- Publication number
- EP0161005A2 EP0161005A2 EP85105887A EP85105887A EP0161005A2 EP 0161005 A2 EP0161005 A2 EP 0161005A2 EP 85105887 A EP85105887 A EP 85105887A EP 85105887 A EP85105887 A EP 85105887A EP 0161005 A2 EP0161005 A2 EP 0161005A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- photoreceptor
- charge generation
- layer
- generation layer
- squarium
- 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.)
- Granted
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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 or 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
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
- G03G5/0611—Squaric acid
-
- 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 or 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
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
Definitions
- This invention relates to novel squarium compounds having a flat photosensitivity in the wide range from visible ray region to the near infrared ray region as a charge generator, a process for preparing them and electrophotographic photoreceptors containing the squarium compounds.
- amorphous selenium or selenium alloys have superior properties as electrophotographic photoreceptors and have been put into practice use.
- a complicated vacuum deposition process is necessary, and further the vacuum- deposited film obtained has a disadvantage in that the film lacks flexibility.
- Zinc oxide is used as a dispersed photographic material in which zinc oxide is dispersed in a resin, but such material has a problem such as a low mechanical strength and cannot be used repeatedly as is.
- Another object of this invention is to provide photoconductive materials having an extremely high photosensitivity, which are possible to use in every electrophotographic process and have a spectral sensitivity in the range from the visible ray region to the near infrared ray region.
- a further object of this invention is to provide extremely superior electrophotographic photoreceptors having a flexibility that inorganic photographic materials fail to have, which are free from drawbacks of organic photographic materials such as polyvinylcarbazole-trinitrofluorenones, that is a low abrasion resistance and lack of mechanical strength, and which are superior in mechanical strength such as abrasion resistance and have a flat spectral sensitivity in the wide range from visible ray region to the near infrared ray region.
- squarium compounds of this invention represented by formula (I) above can be prepared by reacting 3,4-di- hydroxy-3-cyclobutene-l,2-dione (hereinafter referred to as squaric acid) represented by formula (II): with an aniline derivative of formula (III): wherein X, R and n have the same meanings as above.
- the spectral sensitivity of the squarium compounds of this invention show a flat photosensitivity in the range of from 400 to 850 nm, and the squarium compounds of this invention have a sufficient photosensitivity in the range from the entire visible ray region to the near infrared ray region.
- the charge generation layer can consist of a squarium compound alone or a combination of the squarium compound and a binder resin.
- the ratio of the squarium compound of formula (I) to the binder resin used is from about 10% by weight to about 90% by weight, preferably from about 10% by weight to about 50% by weight.
- a solvent coating method and a vacuum evaporation method can be used to prepare the charge generation layer with the squarium compound of this invention without using a binder resin.
- the film thickness of charge generation layer is from about 0.1 u to about 3 ⁇ , preferably from 0.2 v to 1 ⁇ .
- the binder used in the charge generation layer may have or may not have photoconductivity.
- binders having photoconductivity include photoconductive polymers such as polyvinylcarbazoles, polyvinylcarbazole derivatives, polyvinylnaphthalenes, polyvinylanthracenes, polyvinylpyrene, or other organic matrix materials having a charge transport property.
- insulating resins which have not photoconductive property can be used as binders.
- insulating resins include polystyrenes, polyesters, polyvinyltoluenes, polyvinylanisoles, polychlorostyrene, polyvinyl butyrals, polyvinyl acetate, polyvinylbutyl methacrylate, copolystyrene-butadiene, polysulfone, copolysty- renemethyl methacrylate and polycarbonate.
- the binder having dispersed therein a squarium compound is coated on an electroconductive support.
- the coating can be performed by a conventional method such as dip method, spray method, bar coater method and applicator method.
- a good photosensitive layer can be obtained by any of the above methods.
- Usable electrically conductive supports include metals (e.g., aluminum, nickel, chromium, iron, stainless, copper, etc.), paper which is rendered electrically conductive, as well as polymeric films and glass plates having an electrically conductive coat of the above metals, Au, Ag, indium oxide, indium tin oxide, etc.
- metals e.g., aluminum, nickel, chromium, iron, stainless, copper, etc.
- paper which is rendered electrically conductive
- polymeric films and glass plates having an electrically conductive coat of the above metals Au, Ag, indium oxide, indium tin oxide, etc.
- a surface layer such as a protective layer and an insulating layer may further be provided on the light-sensitive layer so as to prevent mechanical damage and chemical change in properties of the light-sensitive layer.
- the protective layer is a layer having low electric resistance of 10 8 to 10 14 ⁇ cm which can be used in so-called Carlson process
- the insulating layer is an electrically insulating layer which can be used in a process as described in U.S. Patents 3,041,167 and 3,438,706. Both layers are substantially transparent to light for exposure and the thicknesses of the protective layer and the insulating layer are about 2 to 20 p and about 10 to 40 u, respectively.
- a barrier layer may be formed between the support and the light-sensitive layer.
- aluminum oxide, nylon, epoxy resins can be used.
- Such a barrier layer may not be formed when the photoreceptor is used in the process of U.S. Patents 3,041,167 and 3,438,706 as described above or when the charge transport layer is formed as a lower layer on the support in the preparation of double- layered photoreceptor (Fig. 2).
- An adhesive layer may also be formed between the support and the light-sensitive layer to improve adhesion therebetween.
- the squarium compound wherein X is a 4-carboxyl group, n is 1 and R is a hydrogen atom was ground with dichloromethane and steel balls for 12 hours.
- the ground compound was then added to a polyester resin (Vylon 200, a tradename) in an amount of 30% by weight based on the weight of the polyester resin, followed by mixing, and then the mixture was coated by an applicator on an aluminum plate to prepare a charge generation layer having a thickness of about 0.5 ⁇ (dry basis).
- a mixture of a polycarbonate resin (Panlite, a tradename) and 1-phenyl-3-[p-diethylamino- styryl]-5-[p-diethylaminophenyl]pyrazoline in an amount of 50% by weight based on the weight of the polycarbonate resin was then coated by an applicator on the charge generation layer to prepare a charge transport layer having thickness of about 15 p.
- the photosensitive surface of this photoreceptor was negatively charged with -6KV of corona electric discharge for 2 seconds using an electrostatic copy paper test instrument manufactured by Kawaguchi Denki Co., Ltd. After it was allowed to stand for 2 seconds in the dark, its surface potential (Vo) was measured and then a light from a tungsten-halogen lamp of illumination intensity of 10 lux was irradiated to the photosensitizer layer. The time when the value of the surface potential changed to a half the original value was determined to obtain a half value of exposure ( ). The results obtained were Vo of 655V and E of 6.5 lux.second.
- the electrophotographic photoreceptors of these examples were prepared in the same manner as described in Example 4 except that, each of the squarium compounds (2) to (6) shown in Table 1 was used, in place of the squarium compound used in Example 4. The electric characteristics of the resulting photoreceptors were determined, and the results obtained are shown in Table 1.
- Electrophotographic photoreceptors with inverted order of the charge generation layer and the charge transport layer were prepared in the same manner as those described in Examples 4 to 9 using squarium compounds (1) to (6) except that the order of the charge generation layer and the transport layer was inverted, and their electric characteristics were measured. The results obtained are shown in Table 2.
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- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59092771A JPS60258556A (ja) | 1984-05-11 | 1984-05-11 | 電子写真用感光体 |
| JP92771/84 | 1984-05-11 | ||
| JP59092769A JPS60260547A (ja) | 1984-05-11 | 1984-05-11 | 新規なスクエアリウム化合物およびその製造方法 |
| JP92769/84 | 1984-05-11 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0161005A2 true EP0161005A2 (fr) | 1985-11-13 |
| EP0161005A3 EP0161005A3 (en) | 1986-12-10 |
| EP0161005B1 EP0161005B1 (fr) | 1989-12-20 |
Family
ID=26434143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19850105887 Expired EP0161005B1 (fr) | 1984-05-11 | 1985-05-13 | Composés de "squarium", procédé de leur préparation et récepteurs électrophotographiques les contenant |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0161005B1 (fr) |
| DE (1) | DE3574866D1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12055851B2 (en) | 2020-09-29 | 2024-08-06 | Samsung Sdi Co., Ltd. | Core-shell compound, photosensitive resin composition including the same, photosensitive resin layer, color filter and CMOS image sensor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508803A (en) * | 1983-12-05 | 1985-04-02 | Xerox Corporation | Photoconductive devices containing novel benzyl fluorinated squaraine compositions |
| US4521621A (en) * | 1983-12-05 | 1985-06-04 | Xerox Corporation | Novel squarine systems |
-
1985
- 1985-05-13 EP EP19850105887 patent/EP0161005B1/fr not_active Expired
- 1985-05-13 DE DE8585105887T patent/DE3574866D1/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0161005A3 (en) | 1986-12-10 |
| DE3574866D1 (de) | 1990-01-25 |
| EP0161005B1 (fr) | 1989-12-20 |
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