EP0324180B1 - Matériau d'enregistrement électrophotographique - Google Patents

Matériau d'enregistrement électrophotographique Download PDF

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Publication number
EP0324180B1
EP0324180B1 EP88121872A EP88121872A EP0324180B1 EP 0324180 B1 EP0324180 B1 EP 0324180B1 EP 88121872 A EP88121872 A EP 88121872A EP 88121872 A EP88121872 A EP 88121872A EP 0324180 B1 EP0324180 B1 EP 0324180B1
Authority
EP
European Patent Office
Prior art keywords
recording material
polyvinylphenol
layer
photoconductive layer
binder
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
Application number
EP88121872A
Other languages
German (de)
English (en)
Other versions
EP0324180A3 (en
EP0324180A2 (fr
Inventor
Erwin Dr. Lind
Franz Freimuth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0324180A2 publication Critical patent/EP0324180A2/fr
Publication of EP0324180A3 publication Critical patent/EP0324180A3/de
Application granted granted Critical
Publication of EP0324180B1 publication Critical patent/EP0324180B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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, 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
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0535—Polyolefins; Polystyrenes; Waxes

Definitions

  • the invention relates to an electrophotographic recording material comprising an electrically conductive layer support, particularly suitable for the production of printing forms or printed circuits, and a photoconductive layer which contains organic photoconductor, phenolic resin as a binder, sensitizer and conventional additives.
  • Recording material of the type described is known (DE-PS 25 26 720 corresponding to US-PS 4,063,948). It contains binders in the photoconductive layer which are soluble in aqueous or alkaline solvent systems. These include high molecular weight substances which carry alkali-solubilizing groups such as acid, anhydride, carboxyl, phenol, sulfonic acid, sulfonamide or sulfonimide groups. Binders with high acid numbers are particularly suitable. With good electrophotographic properties, however, the solubility of the layer is not yet adjusted to meet the highest requirements for reproducing small details.
  • mixtures which contain photosensitive compounds such as o-quinonediazides and phenol condensation products such as novolak. After UV exposure, they experience a change in their solubility in an aqueous alkaline solution through the decomposition reaction of the photosensitive compounds.
  • photosensitive compounds such as o-quinonediazides and phenol condensation products such as novolak.
  • novolak component polymers or copolymers can be used which have vinylphenol units (DE-PS 23 22 230 corresponding to US-PS 3,869,292). Their use for electrophotographic purposes could not be deduced from this.
  • the solution to this problem is based on a material of the type mentioned at the outset, and it is characterized in that an optionally substituted polyvinylphenol is present in the photoconductive layer as a binder.
  • an optionally substituted polyvinylphenol is present in the photoconductive layer as a binder.
  • a polyvinylphenol with a molecular weight between 1500 and 60,000 is present.
  • the polyvinylphenol according to the invention is preferably a polymer of p-vinylphenol.
  • the polyvinylphenol can preferably be halogen-substituted.
  • chlorinated or brominated, in particular brominated, polymers are preferably used as halogenated vinylphenol polymers.
  • copolymers of vinylphenols and other vinyl compounds such as styrene or acrylic acid esters can also be used.
  • the homopolymers of p-vinylphenol are preferred.
  • the halogen content of the halogenated polyvinylphenol is generally between 20 and 60, preferably 40-60 percent by weight.
  • an o-quinonediazide is preferred in the photoconductive layer according to the invention an o-naphthoquinonediazide is present. It is hereby achieved that the photoconductive layer can be subjected to a post-exposure with UV light after the development (emphasis), which results in a particularly good solubility of the exposed areas during the stripping. The applied toner image can not be fixed. It was completely surprising that the addition of the light-sensitive substance does not adversely change the electrophotographic properties of the photoconductive layer and exhibits good charging behavior with little dark discharge. The recording material also has a good shelf life.
  • the photoconductive layer can generally contain 5-40 percent by weight of o-quinonediazide. Preferably 15 to 25 percent by weight is present.
  • the reproduction of fine picture elements, such as fine raster, is made possible in excellent quality.
  • cellulose products such as special papers, cellulose hydrate, cellulose acetate
  • plastics such as polyamides in film form or metal-coated films, are also suitable as layer supports.
  • the surface refinement consists in mechanical or electrochemical roughening and, if appropriate, in a subsequent anodization and treatment with polyvinylphosphonic acid according to DE-OS 16 21 478 in accordance with US Pat. No. 4,153,461. This results in a higher print run and less susceptibility to oxidation.
  • the organic photoconductors used for the photoconductive layer can be regarded as known in principle.
  • Triphenylamine derivatives more highly condensed aromatic compounds, such as anthracene, benzo-fused heterocycles, such as benzothiazoles, pyrazoline, imidazole or triazole derivatives, oxdiazole derivatives such as 2,5-bis- (4'-diethylaminophenyl) oxdiazole-1,3,4), oxazole derivatives such as 2 -Phenyl-4- (2'-chlorophenyl) -5- (4 ⁇ -diethylaminophenyl) oxazole, further vinyl aromatic polymers such as polyvinylanthracene, polyacenaphthylene or polyvinyl carbazole and their copolymers, provided that they are compatible with polyvinylphenol and are suitable for differentiation in solubility.
  • Preferred o-quinonediazides to be added are preferably o-naphthoquinonediazides, such as the di- or tri-esters of 2,3,4-trihydroxybenzophenone and naphthoquinone- (1,2) -diazide- (2) -5-or 4-sulfonic acid, esters , especially the diester of bis (2-hydroxynaphthyl) methane and naphthoquinone (1,2) diazide- (2) -5-sulfonic acid and esters from 2-phenyl-2- (4'-hydroxyphenyl) propane and naphthoquinone- (1,2) diazide- (2) -4 -sulfonic acid.
  • Esters from hydroxyl-containing polymers and naphthoquinonediazide sulfonic acids are also suitable. Mixtures of the quinonediazide sulfonic acid esters mentioned can also be used with good success.
  • Additional binders can also be contained in the photoconductive layer. Their addition serves to improve the film properties of the layer, its adhesive strength on the substrate and to increase the print run.
  • Suitable binders are, for example, copolymers of styrene and maleic anhydride and their partial esterification products, polyvinyl acetates and copolymers with crotonic acid, phenolic resins, coumarone-indene resins, polyacrylates and copolymers with acrylic acid, rosin and its conversion products, maleate resins and phthalate resins.
  • Electrophotographic recording material contains at least one sensitizing dye to expand the spectral sensitivity range.
  • Suitable sensitizing dyes are, for example, malachite green (Color Index (CI) 42,000), crystal violet (CI 42 555), methyl violet (CI No. 42 535), night blue (CI No. 44 085), Victoria blue (CI No. 44 045 or No. 52595: 2), Rhodamine B, Rhodamine FB (CI No. 45 170), Capri Blue (CI No. 51 015), methylene blue (CI No. 52 015), Fuchsin (CI No. 42 500), Rose Bengal (CI No. 45 440), polymethine dyes such as Astrazonorange G (CI No.
  • Astrazonorange R (CI 48 040), Astrazonyellow 3G (CI No. 48 055), Astrazon Yellow 5G (CI No. 48 065), Basic Yellow (CI No. 48 060), or Astrazon Red Violet (CI No. 48 013).
  • the recording material according to the invention can contain leveling agents and plasticizers and / or between layer support and layer adhesion promoter as usual additives in the photoconductive layer.
  • the presence of the additive does not significantly affect the interaction between the photoconductor and any o-quinonediazide present.
  • the solution is applied to a 300 ⁇ m thick electrochemically roughened, anodized and pretreated with polyvinylphosphonic acid aluminum plate in such a way that that after evaporation of the solvent, a photoconductor layer with a thickness of 5.5 microns is formed.
  • the light sensitivity of the layer is determined by charging it to -500 V and exposing it to white incandescent light until it is discharged to a residual voltage of -60 V.
  • the energy density required for this is 320 ⁇ J / cm2.
  • the photoconductor layer is charged with a corona to a surface potential of -500 V and exposed to images in a repro camera with 8 halogen lamps of 500 watts for 20 seconds.
  • the resulting latent charge image is developed using a magnetic roller with a commercially available toner / carrier development mixture.
  • the developed image is fixed with the help of heat radiation.
  • the plate For conversion into a printing form, the plate is immersed for 2 minutes in a solution which is obtained by dissolving 20 g Na2SiO3 ⁇ 9H2O and 2 g NaOH in a mixture of 728 g water, 100 g n-propanol and 150 g ethylenediglycol.
  • the layer parts not covered by the toner image are removed with a water jet with gentle rubbing.
  • the printing form obtained is characterized by good raster and full tone reproduction.
  • the plate prints well over 100,000 prints in a sheetfed offset press.
  • the 50 g poly-p-vinylphenol resin is replaced by a novolak made from m-cresol and Formaldehyde (Alnovol® 429 K from HOECHST AG) gives a printing plate which requires an energy density of 520 ⁇ J / cm2 to discharge from -500 V to -60V and which has to be exposed in the repro camera for 30 seconds.
  • the residence time in the stripping solution described above is 6 minutes.
  • 35 g of 2-vinyl-4- (2'-chlorophenyl) -5- (4 ⁇ -diethylaminophenyl) oxazole and 40 g of polyvinylphenol are dissolved in a mixture of 160 ml of ethylene glycol monomethyl ether, 270 ml of tetrahydrofuran and 60 ml of butyl acetate and the solution is added 440 mg astrazone orange R (CI 48 040) and 350 mg astrazone red violet 3 RN (CI 48 013).
  • the solution is used to coat an anodized aluminum plate which has been roughened by wet brushing and pretreated with polyvinylphosphonic acid in such a way that the photoconductor layer has a weight per unit area of 5.5 g / m 2.
  • the plate is charged (-500 V) and exposed as described in Example 1, the exposure time being only 14 seconds in order to achieve a high-contrast, base-free image.
  • the latent electrostatic image has been made visible with a dry developer and the toner image has been fixed by means of heat radiation
  • the plate is passed through a commercially available stripping device to remove the non-image areas at a throughput speed of 1.1 m / min.
  • the plate is charged to -500 V and imagewise exposed in a repro camera for 18 seconds with 10 halogen lamps of 600 watts each, developed and fixed in a known manner.
  • the photoconductor layer is removed at the areas not covered by toner with the solution described in Example 1.
  • the printing result achieved with the plate is excellent.
  • a 300 ⁇ m thick, electrochemically roughened, anodized aluminum foil treated with polyvinylphosphonic acid is coated with the solution in such a way that a 5 ⁇ m thick photoconductor layer remains after the solvents have evaporated.
  • the layer is charged to -500 V and exposed in a repro camera as described in Example 1.
  • the toner image created after development is not fixed.
  • the concrete plate is exposed for 2 minutes in a commercial automatic copying machine under a 5 KW metal halogen lamp (Violight).
  • the toner image is then removed by rinsing with water and the plate is immersed for 1/2 minute in a stripping solution described in Example 1, rinsed with water and rubbed off.
  • a printing form is obtained in which, in particular, a rastered image is reproduced better than with the plates described in Examples 1-3.
  • An anodized aluminum foil is coated with the solution as described in Example 4.
  • a toner image that is not fixed is produced on the coated film by electrophotography.
  • the toner image is rinsed off with water.
  • the plate is immersed in a decoater solution described in Example 1 for 30 seconds and rinsed with water while rubbing. You get a planographic printing form with very good image reproduction and high print run quality.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (7)

  1. Matériau de reprographie électrophotographique comprenant un support de couche électroconducteur, convenant en particulier à la fabrication de formes d'impression ou de circuits imprimés, et d'une couche photoconductrice contenant des photoconducteurs organiques, une résine phénolique comme liant, un agent sensibilisant et les adjuvants usuels, caractérisé en ce que le liant présent est un poly(vinylphénol) éventuellement substitué.
  2. Matériau de reprographie selon la revendication 1, caractérisé en ce que le liant présent est un poly(vinylphénol) de masse moléculaire comprise entre 1500 et 60000.
  3. Matériau de reprographie selon la revendication 1 ou 2, caractérisé en ce que le poly(vinylphénol) est un polymère du p-vinylphénol.
  4. Matériau de reprographie selon une des revendications 1 à 3, caractérisé en ce que le poly(vinylphénol) est halogéné.
  5. Matériau de reprographie selon la revendication 4, caractérisé en ce que le poly(vinylphénol) est bromé.
  6. Matériau de reprographie selon la revendication 1, caractérisé en ce que la couche photoconductrice contient un o-quinonediazide.
  7. Matériau de reprographie selon une des revendications 1 et 6, caractérisé en ce que la couche photoconductrice contient un o-naphtoquinonediazide.
EP88121872A 1988-01-12 1988-12-30 Matériau d'enregistrement électrophotographique Expired - Lifetime EP0324180B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3800617A DE3800617A1 (de) 1988-01-12 1988-01-12 Elektrophotographisches aufzeichnungsmaterial
DE3800617 1988-01-12

Publications (3)

Publication Number Publication Date
EP0324180A2 EP0324180A2 (fr) 1989-07-19
EP0324180A3 EP0324180A3 (en) 1990-01-17
EP0324180B1 true EP0324180B1 (fr) 1993-07-21

Family

ID=6345116

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88121872A Expired - Lifetime EP0324180B1 (fr) 1988-01-12 1988-12-30 Matériau d'enregistrement électrophotographique

Country Status (4)

Country Link
US (1) US4933248A (fr)
EP (1) EP0324180B1 (fr)
JP (1) JPH01216362A (fr)
DE (2) DE3800617A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5328788A (en) * 1990-07-26 1994-07-12 Matsushita Electric Industrial Co., Ltd. Organic photoconductive material for electrophotography and method for making the same
US5437952A (en) * 1992-03-06 1995-08-01 Konica Corporation Lithographic photosensitive printing plate comprising a photoconductor and a naphtho-quinone diazide sulfonic acid ester of a phenol resin
JPH05323682A (ja) * 1992-05-18 1993-12-07 Konica Corp 印刷版の製版方法
TW403972B (en) * 1993-01-18 2000-09-01 Semiconductor Energy Lab Method of fabricating mis semiconductor device
DE4445820A1 (de) * 1994-12-21 1996-06-27 Hoechst Ag Verfahren zum Entwickeln bestrahlter, strahlungsempfindlicher Aufzeichnungsmaterialien
DE19803564A1 (de) 1998-01-30 1999-08-05 Agfa Gevaert Ag Polymere mit Einheiten aus N-substituiertem Maleimid und deren Verwendung in strahlungsempfindlichen Gemischen
US6214502B1 (en) 1998-07-21 2001-04-10 Lexmark International, Inc. Charge generation layers comprising binder blends and photoconductors including the same
US6376144B1 (en) 2000-08-03 2002-04-23 Kodak Polychrome Graphics, Llc Organic photoconductive composition
US20040043314A1 (en) * 2002-08-30 2004-03-04 Nusrallah Jubran Organophotoreceptors with a fluoran-based compound
KR100916656B1 (ko) 2002-10-22 2009-09-08 삼성전자주식회사 레이저 조사 장치 및 이를 이용한 다결정 규소 박막트랜지스터의 제조 방법
JP4506583B2 (ja) * 2005-06-24 2010-07-21 富士ゼロックス株式会社 コーティング剤組成物、電子写真感光体及びその製造方法、画像形成装置

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE625567A (fr) * 1961-12-04
NL298004A (fr) * 1962-09-22
ZA6807938B (fr) * 1967-12-04
GB1375461A (fr) * 1972-05-05 1974-11-27
JPS51105389A (en) * 1975-03-01 1976-09-17 Kenji Kanezaki Kojundo pp binirufuenoorujugotaino seizohoho
AU507694B2 (en) * 1975-06-14 1980-02-21 Hoechst Aktiengesellschaft Electrophotographic reproduction
GB2014748B (en) * 1978-02-07 1982-06-16 Konishiroku Photo Ind Electrophotographic material for obtaining toner image and process for forming printing plate by using the same
JPS5730829A (en) * 1980-08-01 1982-02-19 Hitachi Ltd Micropattern formation method
US4439516A (en) * 1982-03-15 1984-03-27 Shipley Company Inc. High temperature positive diazo photoresist processing using polyvinyl phenol
DE3313798A1 (de) * 1983-04-15 1984-10-18 Hoechst Ag, 6230 Frankfurt Elektrophotographisches aufzeichnungsmaterial

Also Published As

Publication number Publication date
US4933248A (en) 1990-06-12
DE3800617A1 (de) 1989-07-20
EP0324180A3 (en) 1990-01-17
DE3882509D1 (de) 1993-08-26
JPH01216362A (ja) 1989-08-30
EP0324180A2 (fr) 1989-07-19

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