WO1991004153A1 - Electro-photographically produced offset printing plate with hydrophilic tonered areas and oleophilic untonered areas - Google Patents

Electro-photographically produced offset printing plate with hydrophilic tonered areas and oleophilic untonered areas Download PDF

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Publication number
WO1991004153A1
WO1991004153A1 PCT/EP1990/001540 EP9001540W WO9104153A1 WO 1991004153 A1 WO1991004153 A1 WO 1991004153A1 EP 9001540 W EP9001540 W EP 9001540W WO 9104153 A1 WO9104153 A1 WO 9104153A1
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WO
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Patent type
Prior art keywords
characterized
chemically
printing plate
areas
groups
Prior art date
Application number
PCT/EP1990/001540
Other languages
German (de)
French (fr)
Inventor
Klaus-Peter Jaeckel
Reinhold J. Leyrer
Volker Muench
Peter Strohriegl
Dietrich Haarer
Original Assignee
Basf Aktiengesellschaft
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00Electrographic processes using a charge pattern
    • G03G13/26Electrographic processes using a charge pattern for the production of printing plates for non-xerographic printing processes
    • G03G13/28Planographic printing plates
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/09Colouring agents for toner particles
    • G03G9/0926Colouring agents for toner particles characterised by physical or chemical properties

Abstract

The novel electro-photographically produced offset printing plate comprises an electrically conductive dimensionally stable substrate (A), at least one photoconductive layer (B) and a printing surface (C) composed of hydrophilic, water-bearing, unprinted tonered areas (c1) and oleophilic, colour-bearing printing untonered areas (c2). The novel offset printing plate can be made by the prior art manner making use of hydrophilic toner or toner which can be easily hydrophilised chemically by conversion with suitable reagents, thermo-chemically by heating and/or photo or radio-chemically by irradiation with electromagnetic or particle radiation.

Description

produced by electrophotographic means offset printing plate with hydrophilic and oleophilic areas tonered untoned areas

description

The invention relates to a novel prepared by electrophotographic means offset printing plate having an electrically conductive dimensionally stable substrate and a photoconductive layer.

Moreover, the invention relates to a novel electrophotographic process for the production of offset printing plates.

Offset printing plates and methods for their production on elektrophoto¬ graphically, for example, from EP-A-0131215, EP-B-0031481, EP-A 0 150 419, EP-A 0 162 216 EP-A-0 156 308, EP-A-0131292, EP-A-0152889 or EP-A-0 198 488 known.

For the production of offset printing plates on the known electronic photographic way is usually an electrophotographic

The recording element used comprising an electroconductive support and at least one photoconductive layer, wherein the photochemically conductive layer contains at least one binder, at least one charge carrier-generating compound (sensitizer), at least one charge carrier-transporting compound (photoconductor) and optionally Zusatz¬ materials. As is known, this electrophotographic recording element, for example, is charged electrically positive or electrically negative by a high voltage corona discharge. Thereafter, the electrically charged photoconductive layer is exposed to actinic light image standard, wherein ultraviolet, visible or infrared light can be considered depending on the sensitizer. Through the exposure, the photoconductive layer is electrically conductive in its exposed areas, so that the electrostatic charge previously generated in these areas can be discharged via the electrically conductive support. In this way, an electrostatic latent image on the recording member is created, which can be developed into a visible image with the aid of suitable liquid or solid toner. This technique of imagewise information recording is generally referred to as xerography, the underlying physical process to the recording method is also known under the name "Carlson process". the toner image is then known to be fixed to the photoconductive layer by heating for the production of offset printing plate. Thereafter, the unexposed and therefore toner-free areas of the photoconductive layer are washed away with the aid of suitable developer solvent or stripped. Here, the exposed areas of the photoconductive layer be protected by the fixed toner thereon prior to stripping. The offset printing plate prepared in this known manner generally takes their hydrophobic Tonerbild¬ areas oily printing inks and to their free-defined by the decoating hydrophilic regions water, so that it is suitable for offset typical printing process.

The basic disadvantage of this known method for making an offset printing plate by electrophotographic means is that the betonerte electrophotographic recording element according to the

Fixing the toner image has to be stripped with developer solvents, so that the offset typical differentiation of the printing plate surface in oleophilic or hydrophobic ink-carrying enters printing areas and hydro¬ hydrophilic water-bearing non-printing areas. In this decision-coating step highest care must be taken because otherwise the printing areas are damaged, which naturally has a Ver¬ deterioration of image quality. In addition, only those carriers can be used in this method, which are both electrically conductive and also have a hydrophilic surface, which limits the choices sensitive.

A method for making an offset printing plate on elektrophoto¬ graphically in which the Entschichtungsschritt deleted, are described in EP-A-0289056, EP-A-0 326 132 or EP-A-0326169 forth.

In the process known from EP-A-0289056 a method elektro¬ photographic recording element is used whose photoconductive layer is covered with a specific covering layer. This top layer is hydrophobic and oleophilic in and of itself, but it can be rendered hydrophilic by treatment with suitable chemical reagents, which is referred to in EP-A-0289056 as "oil-desensitization treatment". Hier¬ be hydrolyzed known chemically bonded non-polar functional groups in the top layer at or hydrolyzed, as a result chemically bound polar functional groups are formed which impart the surface of the top layer of hydrophilic water-carrying properties. In the preparation of offset printing plate, the tonered areas of the surface of the top layer of the thereon fixed hydrophobic or oleophilic toner to be protected against the hydrophilization so that ultimately results in an offset printing plate, the printing surface is ink-bearing from hydro¬ hydrophilic water-bearing non-printing untoned areas and consists of oleophilic composed printed tonered areas.

In the process known from EP-A-0326132 process, the photochemically conductive layer of the electrophotographic recording element containing a partially crosslinked binder having chemically bonded non-polar functional groups which can be represented by the "oil-desensitization treat¬ ment" in carboxylic acid groups converted. The purpose suitable chemical reagents are described in detail in EP-A-0 326 132nd

In the process known from EP-A-0326169 process, the photochemically conductive layer of the electrophotographic recording element contains, in addition to the binder with non-polar functional groups which can be converted into carboxylic acid groups, a polymer obtained by heating thermally or by irradiation with electromagnetic radiation photochemically can be chemically crosslinked, and a crosslinking aid. Otherwise, this process is not different from that from EP-A-0289056 or EP-A-0326132 known methods.

The disadvantage of the known from EP-A-0,289,056 method is that the photoconductive layer must be covered by a cover layer of special material composition always what however verschlech the adhesion of the toner particles to the surface of the imagewise exposed electrophotographic recording element concerned when Betonern ¬ tert. As for the process of EP-A-0 326 132 and EP-A-0326169 applies be¬, these are on the use of electrophotographic Auf¬ drawing elements containing zinc oxide photoconductive layers limited. It must also always the Desensibili- tion against oil (oil-desensitization treatment) are carried out in all these processes, in which it can also cause damage to the printing areas of the offset plate.

The object of the present invention is to find a new-prepared elektrophoto- graphically offset printing plate and a new elektro¬ photographic manufacturing process, which no longer have the disadvantages of the known electrophotographic offset printing plates and of the known electrophotographic processes for their preparation longer. Here, the new one is to electrophotographic means manufacturers Asked offset printing plate to be stable circulation and especially having in their surface an excellent differentiation into printing and non-printing areas, so that excellent printed copies can be produced in particularly high circulation. In contrast, the new electrophotographic production method is to provide the new offset plate in a simple and reproducible manner.

The object of the present invention could be solved in a surprising way by the new produced by electrophotographic means Offset¬ printing plate whose printing surface is composed of hydrophilic water-bearing non-printing tonered areas and consists of oleophilic ink-printed untoned areas. At this surprising solution to the use of toners have contributed, what seen for either themselves are hydrophilic or which during or after the preparation of the new hydro¬ offset printing plate can be phil ated.

Accordingly, the object of the present invention is the new offset printing plate produced by electrophotographic means with

A) an electrically conductive dimensionally stable substrate,

B) at least one photoconductive layer, and

C) a printing surface which consists of

C) hydrophilic water-bearing non-printing areas and oleophilic tonered from c 2) printing ink-carrying untoned areas

is composed.

Another object of the present invention, the novel method for making an offset printing plate by electrophotographic means, by

i has) imagewise exposure of an electrically negatively or electrically positively charged electrophotographic recording element which comprises an electroconductive support (A) and at least one photochemically conductive layer (B), to actinic light, thus on the surface (C) of the electrophotographic recording element a latent electrostatic latent image is formed,

ii) developing the latent electrostatic charge image by a toner to form a betonertes image results, iii) fixing the tonered image on the surface (C), whereby the resulting lithographic printing plate, and optionally

iv) post-treating the lithographic printing plate,

wherein the novel method is characterized in that in this case used either a hydrophilic toner or a toner which is rendered hydrophilic in the method step iii) and / or in a post-treatment step iv) on the surface (C).

The following are the new offset plate for brevity produced by electrophotographic means is referred to as "inventive Offsetdruck¬ plate". Accordingly, the new process for the production position of an offset printing plate by electrophotographic means is referred to as "the invention".

The inventively essential feature or the present invention wesent¬ Liche part of the offset printing plate according to the invention is its printing surface (C) which printing of hydrophilic water-bearing non tonered areas (ci) and consists of oleophilic ink-printed untoned areas (c 2) is composed. Accordingly, the non-printing areas (c) of toner particles are formed, which have been applied in known manner to the surface of an electrophotographic recording element. In contrast, the printing areas (c 2) are formed by that part of the surface of a elektro¬ photographic element, which when Her¬ position of the offset printing plate according to the invention was not covered by toner particles.

In the surface of the electrophotographic recording element in turn may be hydrophobic or oleophilic surface of the photoconductive layer (B) or applied to the surface of the photochemically conductive layer (B) from 0.1 to 5 microns thick, electrically iso¬ lierenden oleophilic layer (D) action. Furthermore, the surface by roughening or by incorporating oleophilic polymeric particles such as polymethyl methacrylate, polystyrene or cross-linked phenolic resins can be matted.

The oleophilic properties of the surface are determined by the material composition of the photoconductive layer (B) or the layer (D) set fest¬. Accordingly, all photoconductive layers (B) or layers (D) having a ¬ have upper surface due to their material composition oleophilic, suitable as a component of the offset printing plate according to the invention. However, even photoconductive layers (B) are having a hydrophilic surface as part of the offset printing plate according to the invention into consideration. However, then the particular offset printing plate according to the invention contains necessarily a layer (D) with oleophilic surface.

Regardless of order is what surface (C), they will not be attacked by the offset typical inks. Preferably, the surface (C) is thermally by heating, photo- by reacting with suitable chemical reagents and / or by irradiation with electromagnetic radiation or particle radiation or has been chemically cross-linked radio partially or fully.

The photopolymerizable layer (B) having an oleophilic surface is preferably used as part of the offset printing plate according to the invention.

Examples of suitable photoconductive layers (B), which come as part of the offset printing plate according to the invention into consideration are the customary and known inorganic photoconductive layers (B) of selenium or doped silicon and organic photoconductive layers (B) comprising at least one binder (bi) , at least one charge carrier-producing compound or a sensitizer (b 2), at least one charge-transporting organic or inorganic compound or a photoconductor (b3) and optionally (b ^ additives included.

Examples of suitable binders (bi) are cellulose ethers, polycarbonates, polyester resins, polystyrene, polyvinyl chloride, polymethacrylates, and styrene / acrylonitrile copolymers, of which are the crosslinked particularly preferably used.

Examples of suitable sensitizers (b 2) are known from the aforementioned prior art.

Examples of suitable photoconductor (b3) are zinc oxide, or the conventional and known low molecular weight oxazole derivatives (DE-B-11 20 875), oxadiazole derivatives (DE-B-10 58 836), triazole derivatives (DE-B-10 60 260), azomethines (US-A-3,041,165), pyrazoline derivatives (DE-B-10 60714), imidazole derivatives (DE-B-11 06 559), arylamines (DE-B-27 12 557), 1, 3-Dithiolderivate (DE B-33 38 204), benzotriazole derivatives (EP-A-0131292), Triazolylpyridin- derivatives (EP-A 0 150 419), pyrazolotriazole derivatives (EP-A-0 156 308), Triphenyltriazolderivate (EP-A-0 162,216) or hydrazone derivatives (EP-A-0001599, DE-A-29 19 791 corresponding to US-A-4,367,273 and US-A-4 278 747, GB-A-2 088 074 and DE-A-31 40 571) or the likewise conventional and known older oligo or polymeric polyvinylcarbazoles or Arylaminpolymere (EP-A-0052961) as well as (meth) acrylate polymers and organopolysiloxanes having pendant carbazolyl groups.

If polymeric photoconductor (b ß) is used, then to the concomitant use of binders (bi) can be dispensed with.

Examples of suitable additives (b) are the customary and known leveling agents, wetting agents, fillers and reinforcing fillers, and cross-linking aid such as organic peroxides, organic silanes or epoxy resins.

In the inventive lithographic printing plate, the photoconductive layer (B) is generally from 0.5 to 40, preferably 0.8 to 25, advantageously from 1 to 20 and in particular 1.5 to 15 microns thick.

The preparation of the photoconductive layer (B) of the offset printing plate according to the invention methodology has no special features, but is provides in a conventional prior art manner known herge¬, and their constituents are used in conventional amounts and beka th. Reference may be made to the way patents mentioned.

Examples of suitable layers (D) are layers of crosslinked or uncrosslinked organic polymers such as Cellulseether, polyester resins, polyvinyl chlorides, polycarbonates, polyolefins, styrene copolymers / acrylonitrile and photopolymerized mixtures which in the usual fashion known by uniform exposure of layers of the upstream standing said polymers, photopolymerizable monomers and polymerization initiators photochemically with actinic light is. Moreover, the layers (D) may contain (b) also the materials Zusatz¬ above.

The production of the layers (D) does not methodically Besonder¬ on units, but is usually carried out by casting v ~ ι - ung and drying the wet film thus obtained, after which the egg so .- ,. ιe layer (D) in a customary and known manner, for example, Uj, -: T photochemically polymerization, can be networked.

The lithographic printing plate of the invention comprises a dimensionally stable electrically conductive support. For this purpose, the customary and known aluminum, zinc, magnesium, copper, steel or multi-metal plates, polymer films are metallized surface, such as polyethylene terephthalate films coated with aluminum or electrically conducting special papers into consideration. The preparation of the electrically conductive dimensionally stable substrate (A) has methodically no special features, but by the customary and known methods of manufacture of Metall¬ plates, metallized papers polymer films and electrically conductive Spezial¬.

In the inventive lithographic printing plate of the electrically conductive dimensionally stable substrate (A), the photoconductive layer (B) and, if desired, the layer (D) allocates ange¬ in the order given above the other and firmly bonded together. This arrangement will be customarily referred to as an electrophotographic recording element. The preparation of the electrophotographic recording element methodically has no special features, but it is done in a conventional manner according to the known prior art methods forth.

For the inventive lithographic printing plate, it is advantageous, bonded or fused when the tonered image areas (cj) with the printing surface (C) and / or are chemically bonded, because this results in a particularly wear-resistant offset printing plate according to the invention. Here, the chemical linkage of tonered image areas (ci) in the surface (C) have been accomplished radioactively chemically by reaction with suitable reagents chemically, thermochemically by heating and / or photochemically by irradiation with electromagnetic radiation or particle radiation or.

Moreover, it is according to the invention for the lithographic printing plate of advantage if the toner particles in the tonered areas (cj) bonded or fused together and / or are chemically linked. Here, the chemical linking of the toner particles can be chemically with each other by reacting the toner particles with suitable reagents, thermochemically by heating photo- and / or by irradiation with electromagnetic radiation or particle radiation or may have been accomplished radiochemically.

Furthermore, it is for the inventive lithographic printing plate of advantage if the toner particles in the tonered areas (ci) contain chemically bonded, nonpolar functional groups which photo- be prepared by reacting with suitable reagents chemically, by heating thermo-chemically and / or by irradiation with electromagnetic radiation or radio¬ possible to chemically decompose to form a chemically bonded polar functional groups. Here, it is (cj) contain chemically bonded, polar functional groups for the inventive lithographic printing plate of very beson¬ alia advantageous if the toner particles in the tonered regions which chemically bonded non-polar functional groups originally present in the in the tonered areas (ci) by reacting photo- chemically with suitable reagents, thermochemically by heating and / or by irradiation with electromagnetic radiation or particle radiation, or have been generated radiochemically.

According to the invention are all suitable chemically bonded non-polar functional groups, which generally photo- by reacting with suitable reagents chemically, by heating thermochemically or by irradiation with electromagnetic radiation or particle radiation or radio-chemically converted into chemically bonded, polar functional groups can be converted. Thus, according to the invention are suitable for Verwendungs¬ purpose of all those non-polar functional groups, which have the above-mentioned Eigenεchaftsprofil. These nonpolar funktio¬ tional groups in the tonered areas (ci) to be bonded to the pigments for coloring, originally used the surfactants to stabilize and / or to the substances for the charge control for the manufacture of concrete unimaged regions (cj) toner particles.

Examples g <- suitable chemically bonded non-polar functional groups sir. from EP-A-0019770 (DE-A-29 22 748), the EP-A-0289056, DE-A-37 21 741, EP-A-0 326 132, EP-A -0134574, EP-A-0101587 or EP-A-0 326 169 or from the article by Ito et al., "A Sensitive Deep UV resist system", in SPE Regional Technical Conference, Ellenville, New YORK, Nov. 1982 and the US-A-4491628 is known.

Examples of particularly suitable nonpolar chemically bound funktio¬ tional groups are carboxylic, sulfonic or Phosphonsäureanhydridgruppen; the anhydrides of acid sulfate or Phosphatestergruppen; Carboxylic, sulfonic, phosphonic, sulfuric or Phosphorsäureestergruppen; Silyl and Silylesterςruppen; Aryl, alkyl and Arylalkyloxycarbonyla inogruppen; N-cyclohexyl-carbodiimide; o-Nitrobenzylacrylatgruppen; tert Butoxicarbonylgruppen; o-quinonediazide groups; epoxy groups; cyclic acetal groups or other groups containing at least two sterically closely spaced hydroxyl groups, which are connected to a single, at least difunctional protecting group; and ethylenically unsaturated photopoly erisierbare and / or radiochemically crosslinkable groups. Chemically bonded, polar functional groups which are suitable for erfindungs¬ proper use, are in particular polar groups funktio¬ nelle which the pigments for coloring, the control-surface-active substances to stabilize and / or substances for the charge for the preparation of the concrete unimaged regions (ci) ursprüng¬ toner particles used Lich are attached and confer the tonered areas (cj) hydrophilic properties. Thus, all those polar functional groups are suitable for use according to the invention which have this property profile.

Examples of highly suitable to be used according to the invention chemically gebunde¬ ner polar functional groups are carboxylic, sulfonic and phosphonic acid groups, acidic sulfur and Phosphorsäureestergruppen, amino and hydroxyl groups and polyalkylene oxide, especially polyethylene oxide groups, of which the hydroxyl groups and polyethylene oxide groups are of particular advantage and are therefore according to the invention with particular preference.

For the inventive lithographic printing plate, it is also especially advantageous when the tonered areas (ci) large amounts, ie 10 to 90.%, Based on the tonered regions (cj), contain hydrophilic inorganic oxides and / or chalcogenides. Here, fumed silica and alumina especially advantageous. They are therefore the invention very particularly preferably used.

Another particular advantage is obtained for the inventive lithographic printing plate, if at least the oleophilic ink-printed untoned areas (c 2) of its printing surface (C) are frosted.

The essential for the invention printing surface (C) the proper offset printing plate erfindungs¬ can be produced in any desired manner. However, it is of particular advantage to the printing surface (C) of the inventive process to produce.

The inventive method proceeds from the above-described in detail electrophotographic recording element comprising at least one electrically conductive dimensionally stable substrate (A), at least one photoconductive layer (B) and optionally the layer (D). This electrophotographic imaging member is in a conventional manner after its manufacture by means of a Hochspannungscorona- discharge electrically negatively or electrically positively charged and thereafter imagewise exposed to a reprographic camera, or a computer-controlled laser, which is known to a latent elektro¬ latent image is formed.

This latent electrostatic image is then known betonert by means of a liquid or solid toner, whereby a betonertes image results.

According to the invention, a toner is used herein confer the toner particles to tonered areas (ci) of the offset printing plate according to the invention after its preparation, hydrophilic water-carrying properties. Thus, either hydrophilic toner or toner to be used for the inventive method, which are hydrophilic at the fixing of the toner or in the aftertreatment of the resulting lithographic printing plate according to the invention, that is, obtained hydrophilic water-carrying properties. This ensures that the concrete unimaged regions (ci) of the thus obtained printing surface (C) do not perform offset printing inks but water when using the proper offset printing plate erfindungs¬ and thus unable to print.

those toners are preferred for the inventive method, which are philiert hydro¬ only during the process of the invention.

In the inventive method, the thereby resulting betonerte image on the surface of the electrophotographic recording element is fixed to the Betonern the latent electrostatic charge image.

This step may be followed by an appropriate post-treatment step.

The toner preferably used in the inventive method, which are hydrophilic in fixing and / or in a post-treatment step, which contain chemically bonded non-polar functional groups described above in detail, from which, by reacting with suitable reagents chemically, by heating thermo-chemically and / or by irradiation photo- with electromagnetic radiation or particle radiation or radiochemically be essential for the function of the offset printing plate according to the invention chemically bonded polar functional groups prepared. The content of the present invention preferably toner to be used in these chemically bound and polar functional groups is generally adjusted so that results in the hydrophilic water-bearing properties of concrete unimaged regions (ci) in the course of the process. The appropriate content of the erfindungs¬ preferred according to the toner to be used of chemically bonded non-polar functional groups can by those skilled easily based on preliminary experiments or simple considerations can be determined by, for example, from EP-A-225 547 or DE-A-38 21 199 known fixed or known from US-A-4,661,431 liquid toner in a conventional manner using pigments for coloring, oberfächenaktiven Substan¬ zen to stabilize and substances for charge control, which contain the non-polar functional groups described in detail, manufactures. Here, it can, for example, from EP-A-0 326 132, EP-A-0 326 169, EP-A-0289056, DE-A-37 21 741, US-A-4,491,628 , EP-A-0101587, EP-A-0134574, and use of the EP-A-0019770 the known high and low molecular materials for the preparation of the respective toner particles, wherein these substances, the function of the surfactants to stabilize and / or the substances can take charge control. The appropriate content of non-polar functional groups, the skilled person may then be easily recognized by the fact that the resultant according to the preliminary tests toner still have the essential for its function as a toner properties, while at the same time chemically by reaction with suitable reagents, thermochemically by heating or by irradiating elektro¬ radiation or particle radiation photo- or can be rendered hydrophilic radiochemically. Therefore, the skilled person with respect to such two boundary conditions can receive the toner more preferably used for the inventive process either by variation of the conventional toner, or he can choose one of the customary and known toners.

In the inventive method particularly those toner of the type described above are used, large amounts, di 10 to 90 wt.%, Based on the toner, included in finely divided hydrophilic inorganic oxides and / or chalcogenides, in particular pyrogenic silica and / or alumina, ,

In the inventive method, the particularly preferred ver¬ used toner particles in the fixing with the surface of elektro¬ photographic element and / or be glued or fused or chemically by reaction with suitable reagents, by heating thermo-chemically and / or by irradiation with electromagnetic radiation or particle radiation photo- or radiochemically connected. This can also be done during the post-treatment step or be completed. According to the invention, the above-described steps in detail non-polar functional groups are chemically bonded in the proper for the function of the offset printing plate erfindungs¬ essential chemically bonded polar functional groups, in particular to the carboxylic, sulfonic or phosphonic acid groups in the implementation of these two Verfahrens¬, converted into the acidic sulfur or Phosphorsäureestergruppen, in the A ino- and hydroxyl groups or polyalkylene oxide groups in the.

The choice of methods of adhesive bonding or fusion or chemical linking of the toner particles with the surface of elektro¬ photographic element and / or with one another, the skilled person can easily make reference to the present in the toner particles chemically bonded non-polar functional groups. He will be beispiels-

amino groups, the carboxylic, sulfonic and Phosphonsäureanhydridgruppen, the anhydrides or acid sulfate Phosphatestergruppen, the carboxylic, sulfonic, phosphonic, sulfuric or Phosphorsäureestergruppen that silyl ether and silyl ester groups, the aryl, alkyl and Arylalkyloxycarbonyl- that N-cyclohexyl-carbodiimide groups, epoxy groups, cyclic acetal groups or other groups containing at least two sterically closely spaced hydroxyl groups, which comparable with a single, at least difunctional protecting group are chemically connected by reacting with suitable reagents,

the epoxy groups by heating thermally,

the o-Nitrobenzylacrylatgruppen comprising tertiary Butoxicarbonylgruppen, the o-quinonediazide group or the ethylenically unsaturated groups by exposure to electromagnetic radiation photochemically or

the ethylenically unsaturated groups by exposure to radiation Partϊkel- radiochemically

realize. To this end, it can also add to the toner particles still suitable crosslinking aids such as photopolymerization initiators, initiators of the thermal radical polymerization, organic silanes or epoxy resins.

For the inventive process it is of very particular advantage when the toner particles are also hydrophilic in which executed in the above manner bonding or fusing and / or in the chemical linkage. For the inventive process it is also particularly advantageous if the surface of the electrophotographic recording element voltage discharge corona by mechanical or electrical roughening by means of a high- and / or is frosted by incorporating finely divided organic fillers.

For the Betonern of the electrophotographic recording element used in the inventive method, the conventional methods and apparatus can be applied to Betonern with solid or liquid toners, eg the device Elfasolautomat® EA 692 from Hoechst, the device OPC® 200 from Polychrome or preferably the Performer® the company Chemco Engineering.

For heating the tonered in the novel procedure electrophotographic recording element per se known methods and equipment can be used in the erfindungs¬ modern methods also. Exemplary heating in drying ovens or irradiation may be mentioned with infrared lamps.

Also for irradiating the tonered electrophotographic Aufzeich¬ voltage elements with electromagnetic radiation or particle radiation with the customary and known methods and apparatuses can be used. exemplified the apparatus with sources of X-ray radiation, ultraviolet radiation, visible light or electron beams as they are commonly used in the field of reprographic or X-ray or electron beam lithography are.

Similarly, the appropriate reagents used in the inventive process are customary and known. Their selection depends primarily on the conditions present in the toner particles chemically bonded non-polar functional groups on the one hand and according to the therefrom produced chemically bonded polar functional groups anderer¬ hand. Furthermore, this suitable reagents either a component of the toner particles may be, or may in the course of fixing and / or the fixing of the toner particles on the surface of the elektrophoto¬ light-sensitive element and / or in the aftertreatment of the offset printing plate according to the invention in a suitable manner as gases, as solids or be added in the form of solutions. Here, their addition in the form of aqueous or organic solutions is preferred.

At the appropriate chemical reagents, it is accordingly acidic or basic, oxidizing or reducing action, ko plexierende or non-complexing, organic, inorganic or organometallic substances, mixtures thereof or aqueous or organic solutions, of which the solutions are preferably used.

Examples of suitable chemical reagents are alkanecarboxylic acids and mineral acids and their salts, alkali metal and alkaline earth metal hydroxides and alkoxides, organic amines, ammonia, compounds having two or more chelating functional groups such as nitrilotriacetic acid and its salts, epoxides, organic silanes, boranes and radical generator Verbin ¬ compounds as initiators of the thermal free-radical polymerization and photopolymerization.

Further examples of highly suitable chemical reagents are shown in the EP-A-0136132.

The treatment of the tonered electrophotographic Aufzeichnungs¬ elements and / or the offset printing plate according to the invention with these solutions is carried out in conventional manner, for example by immersion of the electrophotographic recording elements in question and / or the offset printing plates according to the invention in these solutions, or by spraying the electrophotographic recording elements and / or of offset printing plates according to the invention with these solutions.

Insofar, the inventive method using these solutions is carried out, the offset obtained in this invention is the printing plate in a conventional manner, for example in a forced air drying oven dried.

Preferably, the inventive method using the methods and apparatuses for irradiating with electromagnetic radiation is guided that is photochemically, as well as described above using the corresponding toner particles, which comprise the corresponding surfaces photoempfindl chemically bonded non-polar functional groups durch¬. Here, one can do without any treatment with stripped solutions or with chemical reagents.

The offset printing plate of the invention has particular advantages in their manufacture and their use. So in their manufacture no longer Entschichtungsschritt is necessary, in which it is widely accepted to cause damage or even the peeling of the pressure which parts of the offset plate. Furthermore, the offset printing plate according to the invention can be adapted in practice very easily passed vorge Druckbedindungen. In addition, the offset printing plate according to the invention allows in contrast to the conventional easily the production of printed products, which are related to the image to be multiplied template "negative". This is because in the conventional produced by electrophotographic means offset printing plates, the concrete unimaged regions ultimately form the oleophilic ink-printing areas, whereas this is in the proper erfindungs¬ offset printing plate precisely not the case. This results in application possibilities that could not be realized with known produced by electrophotographic means offset printing plates to date.

Also, the inventive method has particular unexpected advantages. It can be both in terms of the electrophotographic recording elements which operates ver¬ by the inventive process, as well as in terms of its possibilities Ausgestaltungs- extremely variable and adaptable. The inventive method allows therefore Offset¬ invention produce printing plates which are suitably adapted in practice to the respective Anwendungs¬ in an excellent manner.

The offset printing plate according to the invention, but especially the prepared by the novel method are also elements those Bild¬ which can be reproduced otherwise difficult reliable, top-quality again. When printing on an offset printing with offset printing inks of the type "oil-in-water" while its non-printing areas (cj) accept the printing areas (c 2) of its printing surface (C) the oily colors hervor¬ outstanding at, excellent wasser¬ leaders are , In this way results in an excellent contrast and a highly precise pressure, which results in an overall excellent print products. As the offset printing plate has long life under the pressure conditions of an advanta- way, a high printing is also achieved.

Examples

For the following examples three electrophotographic Auf¬ were prepared by the following general instructions drawing elements:

I. Preparation of electrophotographic recording elements; General experimental procedure:

Il The preparation of poly (6-N-carbazolylhexyl methacrylate)

In a heated 500 ml three-necked flask, 200 ml of a solution of 9-borabicyclo were [3.3.1.] Defines vorge nonane (9-BBN) in tetrahydrofuran (0.5 mol / l). After dropwise addition of a solution of 100 mrnol N-5-Hexenylcarbazol in 100 ml of dry tetrahydrofuran, the resulting reaction mixture was stirred for 3 hours at room temperature. Then, in succession

60 ml of ethanol, 20 ml of 6-normal sodium hydroxide solution and 40 ml of hydrogen peroxide (30% strength) was added to the reaction mixture. After one hour of heating at reflux for working up the reaction mixture 200 ml of water were added and then the tetrahydrofuran was removed. The RECT, N- (6-hydroxyhexyl) carbazole was extracted with ether and the ether solution was dried and evaporated. (9: 1) Thereafter, the crude product resul¬ animal still from hexane / acetone is recrystallized. This in

61% yield obtained pure N- (6-hydroxyhexyl) carbazole was in the form of white crystals.

To a solution of 25 mrnol N- (6-hydroxyhexyl) carbazole and 30 mmoles tri- ethylamine in 100 ml of dry dichloro a solution of 30 mrnol methacrylic acid chloride in 10 ml dichloromethane was added dropwise ethane. Then the reaction mixture was stirred for 3 hours at room temperature and then washed for working with 2-normal sodium hydroxide solution and water. The formed 6- (N-carbazolyl) was hexyl methacrylate tion mixture after concentration of the Reak¬ by column chromatography on silica gel (eluent: dichloromethane) was isolated. The thus obtained in a yield of 70% 6- (N-carba zolyl) hexyl methacrylate was present as a colorless oil and had the following key data:

IR (film): 1715 cm "1 (ester), 1635 cm" 1 (C = C)

1625, 1595, 750, 720 cm -1 (carbazole)

1H-NMR (CDC1 3): δ = 1.3-1.9 (m), 4.02 (t), 4.23 (t), 5.46 (m), 6.00 (m),

7.1-7.2 (m), 7.3-7.5 (), 8.0-8.1 (m) intensity ratio: 11: 2: 2: 1: 1: 2: 4: 2 17, 6 mrnol 6- (N-carbazolyl) hexyl methacrylate and 0.18 mrnol azobisisobutyronitrile were dissolved in 50 ml of dry toluene. The solution was degassed and then heated for 48 hours under stirring to 60 ° C. After cooling, the polymer obtained from the solution by addition of methanol and was precipitated for further purification twice from chloroform / methanol reprecipitated. In this way, Pol was (6-N-carbazolylhexyl methacrylate) in a yield of 88% was obtained. The polymer was characterized by IR spectroscopy and GPC. The characteristic data are given below.

IR (film): 1720 cπT 1 (ester), 1625, 1595, 750, 720 cm "1 (carbazole)

Gel permeation chromatography, GPC: The GPC (polystyrene standard) determined molecular weight was 66,000 (M w: 84,000, M n: 28,000,

Figure imgf000020_0001

In this manner, much has been of poly (6-N-carbazolyl methacrylate) herge¬ provides that the quantity for the production of electrophotographic recording elements sufficient.

1.2 Preparation of the electrophotographic recording elements

containing from accordance with Clause carbazolyl side groups produced 1.1 polymethacrylate, three 14% solutions prepared in tetrahydro- furan. These solutions were poured after filtration on three selenbedampfte carrier foils and the tetrahydrofuran was evaporated. The resulting three photoconductor layers had a thickness of 10 microns after drying. In the selenbedampften carrier film it was a 100 μ thick polyethylene terephthalate film that was vapor coated with a thin aluminum layer. The vapor-deposited on the aluminum selenium layer had a thickness of about 1 micron.

It resulted elements three identical electrophotographic Aufzeichnungs¬, adhered where the photoconductor layers containing from carbazolyl side groups polymethacrylate firmly on the selenbe¬ deposited carrier films and elements even when bending the Aufzeichnungs¬ not break or flaking. The electrophotographic recording elements had the following, measured in a conventional manner according to the Carlson process performance properties to:

• maximum potential acceptance E max: 229 kV / m • dark decay for 20 seconds after the electrostatic charge: 8%

• Photo drop, caused by the full-surface 5 seconds lasting 5 exposure to visible light: 80%

example 1

Producing an offset printing plate according to the present invention 10 according to the invention method using a liquid toner which can be rendered hydrophilic photochemically; Experimental method:

1.1, which contains chemically bonded non-polar functional groups, The preparation of the liquid toner which provide 15 chemically bonded polar functional groups upon exposure to UV light; Versuchs¬ regulations:

First, from

20 1400 g of white spirit (Isopar H from Exxon)

283 g of a customary and known Rosins (rosin), 557 g of the diazo resin of the formula

Figure imgf000021_0001
which had been prepared by partial esterification of a p-cresol novolak with l, 2-naphthoquinone-2-diazide-4-sulfonyl chloride 5 by weight and a 1,2-naphthoquinonediazide-content of the 65th auf¬ pointed% (of the company PCAS RP2 ), 168 g of an ethylene-vinyl acetate copolymer (AC 400 from

Allied Corp.), 168 g of an ethylene-acrylic acid copoly older (AC 540 Allied), 0 200 g of an aluminum oxide pigment with a mean particle size of <1 micron, and 83 g of a phthalocyanine pigment, by lOminütiges stirring in an impeller stirrer at a speed of 8000 revolutions per minute (rpm), a mixture prepared at a temperature of 70 to 80 ° C.

This mixture was made in the impeller agitator with a speed of 8000 rpm at 70 to 80 ° C for 10 minutes with 2000 g of a latex

1000 g of a gasoline (Isopar H from Exxon)

50 g of a stabilizer (polymer of, based on the poly erisat, 40 wt.% Of o-nitrobenzyl, 56 wt.% Acrylate Laurylmeth- and 3 wt.% Glycidyl methacrylate, which with 1 wt.% Of methacrylic acid was esterified) and 950 g latex particles (0.4 to 1 micron-sized particles of a polymer of, based on the polymer, 45 wt.% of o-nitrobenzyl, 52 wt.% of methyl methacrylate and 3 wt.% methacrylic acid)

and 670 g of a stabilizer solution

Isopar H and the above-mentioned stabilizer

Figure imgf000022_0001

The hereby resulting mixture was added still with 3700 g of Isopar H, and thereafter stirred at a temperature of 50 to 55 ° C for 30 minutes in the impeller stirrer at 1500 rpm. Hereinafter, were 9061 g of a so-called before predispersion, which dispersion for producing the actual Toner¬ were ie of the liquid toner used.

To this was added

920 g of the predispersion,

56 g of carnauba wax,

60 g of the polymer dispersion Neocryl EX 550 from Polyvinyl Chemical Industries, Division of Beatrice, and

822 g of Isopar H

mixed in a ball mill at a speed of 300 rpm at room temperature. After mixing, a further 1000 g of Isopar H were added.

The liquid toner thus obtained was further heated at 60 ° C for 30 minutes, after which it was ready for use. 1.2 The implementation of the method according to the invention; experimental procedure

One of the three electrophotographic recording elements was charged in a conventional manner with a DC voltage corona from a distance of 1 cm within 20 seconds and thereafter exposed imagewise in a reprographic camera with visible light. The resulting charge this picture was betonert phoretisch in the liquid toner unit Performer® the company Chemco engineering electro in a conventional manner.

The betonerte electrophotographic recording element was dried and then shortly heated to 130 ° C, so that the toner particles fused together and to the surface of the electrophotographic recording element or bonded.

Subsequently, the betonerte electrophotographic was Aufzeich¬ voltage element in a Röhrenflachbelichter (emission maximum in the wavelength range Wellen¬ n of λ = 350 to 420) for 2 minutes over the entire surface irradiated with UV light. In this case, both the o-Nitrobenzylacrylatgruppen as well as the 1, 2-naphthoquinonediazide groups in the tonered areas of the electrophotographic recording element with the formation of chemically bound carboxylic acid groups (polar functional groups) have been cleaved, whereby the tonered areas have been rendered hydrophilic and resulted in the offset printing plate according to the invention.

The offset printing plate according to the invention was mounted on a printing cylinder and used in an offset printing using a conventional and known offset printing inks of the type "oil in water" for the production of printed products.

Here, the oleophilic or hydrophobic ink-printed untoned areas on took (c 2) of the printing surface (C) the proper offset printing plate erfindungs¬ oil paints excellent, whereas the hydro¬ hydrophilic water-bearing non-printing areas (ci) remained completely free of ink. Characterized resulted in large numbers quite excellent Druck¬ products which faithfully reproductions the design of the template used for imagewise exposure in the finest picture elements. In game 2

Producing an offset printing plate according to the invention by the inventive process using a liquid toner, 5 which can be rendered hydrophilic photochemically; Experimental method:

Example 1 was repeated, except that, by weight for the manufacture of the liquid toner in place of the diazo resin described in Example 1, a polymer composed of, based on the polymer, 50 wt.% Of o-nitrobenzyl 45th% 0 methyl methacrylate and 5 wt.% Methacrylic acid was used ,

The lithographic printing plate obtained according to the invention had the same hervor¬ superior performance properties as that of Example 1. Fig.

Example 3 15

Producing an offset printing plate according to the invention by the inventive method using a solid two-component toner, which can be rendered hydrophilic photochemically; 0 experimental procedure:

3.1, which contains chemically bonded non-polar functional groups, The preparation of the solid toner which provide chemically bonded, polar functional groups upon exposure to UV light; Experimental 25 rule:

In a mixer 80 parts by weight of a polymer can be made from, based on the polymer, 50 wt.% Of o-nitrobenzyl, 30 wt.% Styrene and 20 wt.% Butyl ethacrylate, 15 parts by weight of very finely ground Al2O3 (mean particle size 30 <1 micron), 4 parts by weight of carbon black and 1 part by weight of stearyl pyrrolidino [l, 2-α] benzimidazolium bromide (see FIG. DE-A-38 21 199) are intensively mixed, kneaded at 120 ° C , extruded and pre-ground.

By grinding in a fluid-bed opposed jet mill with classifier wheel 35 and subsequent sifting toner particles are formed from 5 to 25 microns with a mean particle size of 15 microns.

To prepare the so-called Developers 1 part by weight of Toner¬ were particles with 99 parts by weight of an iron powder with particle sizes between 40 75 and 175 microns, a mean particle size of 120 microns and spherical shape accurately weighed and for 10 minutes on a roller block activated. 3.2 The implementation of the method according to the invention; Experimental method:

The third electrophotographic recording element was prepared as in Example 1, Section 1.2 describes charged and exposed imagewise. The resulting electrostatic latent image was betonert in the conventional dry toner handels¬ device "Elfasolautomat® EA 692" from Hoechst, using the activated developer in accordance with paragraph 3.1 prepared. Thereafter, the betonerte electrophotographic recording element was prepared as in Example 1, Section 1.2 describes further processed to the erfindungs¬ proper offset printing plate. This had the same outstanding performance properties such as offset printing plates erfindungs¬ contemporary of Examples 1 and 2. FIG.

Claims

claims
1. prepared in electrophotographic means offset printing plate
A) an electrically conductive dimensionally stable substrate,
B) at least one photoconductive layer, and
C) a printing surface which consists of
C) hydrophilic water-bearing non-printing tonered
Areas and oleophilic c 2) ink-carrying untoned areas
is composed.
2. The offset printing plate according to claim 1, characterized in that the photoconductive layer (B) thick of a 0.1 to 5 microns, electrically insulating, oleophilic layer (D) is covered whose untoned surface areas oleophilic ink-printed untoned areas (c form 2) of the printing surface (C).
3. The offset printing plate according to claim 1 or 2, characterized in that the tonered areas (ci) with the surface (C) bonded or fused and / or chemically connected are.
4. The offset printing plate according to claim 3, characterized in that the chemical linkage of tonered areas (ci) with the surface (C) chemically by reaction with suitable reagents, thermochemically and / or by heating by exposure to elektro¬ radiation or particle radiation photo or has been chemically radio¬ accomplished -.
5. The offset printing plate according to any one of claims 1 to 4, characterized in that the toner particles in the tonered areas (ex) bonded or fused together and / or chemically connected to each other.
6. The offset printing plate according to claim 5, characterized in that the chemical linking of the toner particles to one another chemically by reaction with suitable reagents, has been accomplished chemically and / or photochemically by irradiation with electromagnetic radiation or particle radiation or radiochemically by heating thermo¬.
7. The offset printing plate according to any one of claims 1 to 6, characterized in that the tonered image areas (ci) of chemically bonded non-polar functional groups, which by reaction with suitable reagents chemically, by heating thermo¬ chemically and / or by irradiating with electromagnetic radiation or particle radiation can be converted photo- or radiochemically in chemically bonded, polar functional groups.
8. The offset printing plate according to any one of claims 1 to 7, characterized in that the tonered image areas (ci) chemically bonded, polar functional groups, which consists of chemically bonded non-polar functional groups by reaction with suitable reagents chemically, by heating thermochemically and / or by irradiation with electromagnetic radiation or particle radiation photo- or have been generated radiochemically.
9. The offset printing plate according to any one of claims 1 to 8, characterized in that at least the untoned areas (c 2) of the
Surface (C) are frosted.
10. A method for making an offset printing plate by
i) imagewise exposure of an electrically negatively or electrically positively charged electrophotographic Aufzeichnungs¬ elements, which an electrically conductive dimensionally stable substrate (A) and at least one photoconductive layer (B) auf¬ has, to actinic light, thus on the surface (C) of the electrophotographic is generated recording member, a latent electrostatic charge image,
ii) developing the latent electrostatic charge image by a toner, thereby resulting in a betonertes image on the surface (C), iii) fixing the tonered image, whereby the offset printing plate is obtained, and optionally
iv) post-treating the lithographic printing plate,
characterized in that this uses a hydrophilic toner or a toner which is rendered hydrophilic during said step iii) and / or during the post-treatment step iv) on the surface (C).
11. The method according to claim 10, characterized in that in this case heated for the purpose of fixing in step iii) the betonerte image, is reacted with suitable chemical reagents and / or irradiated with electromagnetic radiation or particle radiation.
12. The method of claim 11, characterized in that the mixture is heated in the aftertreatment iv) the offset printing plate, reacted with suitable reagents and / or irradiated with electromagnetic radiation or particle radiation.
13. The method according to any one of claims 10 to 12, characterized gekenn¬ characterized in that the photoconductive layer (B) thick of a 0.1 to 5 microns, electrically insulating, oleophilic layer (D) is covered whose untoned surface areas after the method step iii) or the post-treatment step iv) the oleophilic ink-printing areas (c 2) of the surface (C) form.
14. The method according to any one of claims 10 to 13, marked thereby characterized, that treatment step in method step iii) and / or in posttreatment iv) the toner particles by reacting with suitable reagents chemically, by heating thermo-chemically and / or by exposure to electromagnetic radiation or with radiation Partikel¬ photo- or radiochemically hydrophilic.
15. The method according to any one of claims 10 to 14, characterized gekenn¬ characterized in that step in step iii) or in Nachbehandlungs¬ iv), the toner particles adhered to each other or fused and / or by reacting with suitable reagents chemically, by heating and thermochemically / or photo- by irradiation with elektro¬ radiation or particle radiation or radiochemically together.
16. The method according to any one of claims 10 to 15, characterized gekenn¬ characterized in that in this case used solid or liquid toner whose toner particles contain chemically bonded, polar functional groups.
5
17. The method according to any one of claims 10 to 15, characterized gekenn¬ characterized in that in this case used solid or liquid toner having toner particles which contain chemically bonded, nonpolar groups which, in method step iii) and / or in post-treatment step iv)
10 provide chemically bonded, polar functional groups by reacting with suitable reagents chemically, by heating thermo-chemically and / or photochemically by irradiation with electromagnetic radiation or particle radiation or radiochemically.
15 18. The method according to claim 17, characterized in that it is in the chemically bonded non-polar groups are carboxylic, sulfonic and Phosphonsäureanhydridgruppen; to anhydride groups of acidic sulfate or Phosphatester; phorsäureestergruppen to carboxylic, sulfonic, phosphonic, sulfuric and phosphoric; silyl ether and silyl ester groups to; 0 to aryl, alkyl or Arylalkyloxycarbonylaminogruppen; imide groups to give N-cyclohexyl carbodi; to o-Nitrobenzylacrylatgruppen; o-quinonediazide groups; epoxy groups; cyclic acetal groups or other groups containing at least two sterically closely spaced hydroxyl groups, which are connected to a single, at least doubly functional 5 protecting group; and acts to ethylenically unsaturated groups.
19. The method according to any one of claims 16 to 18, characterized gekenn¬ characterized in that it is in the chemically bonded polar functional 0 tional groups are carboxylic, sulfonic and phosphonic acid groups; acidic sulfuric and Phosphorsäureestergruppen; groups to amino and Hydroxyl¬; and dealing with alkylene oxide.
20. The method according to any one of claims 10 to 19, characterized marked 5 is characterized in that it is at the appropriate chemical reagents, aqueous or organic solutions of acidic or basic, oxidizing or reducing action, complexing or non-complexing, organic, inorganic, and organometallic materials, or acts around the respective pure substances themselves or mixtures thereof 0.
21. The method of claim 20, characterized in that it is for the fabrics to alkanecarboxylic acids and mineral acids and their salts; alkoxides to alkali and alkaline earth and; organic amines and ammonia; compounds having two or more chelatisieren-
5 shows the functional groups; concerns epoxides and to radical yielding substances.
22. The method of claim 20 or 21, characterized in that the substances in question are contained in the toner particles.
10
23. The method according to any one of claims 10 to 22, characterized characterized gekenn¬ that the toner particles contain large amounts of finely divided hydrophilic inorganic oxides and / or chalcogenides.
15 24. The method according to claim 23, characterized, in that the
Toner particles of fumed silica and / or aluminum oxide.
25. The method according to any one of claims 10 to 24, characterized characterized gekenn¬ that the surface (C) at least in its untoned
20 is matted areas (c 2).
26. Offset printing plate according to any one of claims 1 to 9, characterized gekenn¬ characterized in that they have been prepared according to the method of any one of claims 10 to 25th
25
30
35
40
PCT/EP1990/001540 1989-09-13 1990-09-12 Electro-photographically produced offset printing plate with hydrophilic tonered areas and oleophilic untonered areas WO1991004153A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DEP3930584.8 1989-09-13
DE19893930584 DE3930584A1 (en) 1989-09-13 1989-09-13 produced by electrophotographic means offset printing plate with hydrophilic and oleophilic areas tonered untoned areas

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19900913378 EP0491761B1 (en) 1989-09-13 1990-09-12 Electro-photographically produced offset printing plate with hydrophilic tonered areas and oleophilic untonered areas
DE1990510226 DE59010226D1 (en) 1989-09-13 1990-09-12 produced by electrophotographic means offset printing plate with hydrophilic and oleophilic areas tonered untoned areas
FI920474A FI920474A0 (en) 1989-09-13 1992-02-04 Elektrofotografiskt framstaelld press plate, with the hydrophilic tonade omraoden Science oleofiliska otonade omraoden.

Publications (1)

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JP (1) JPH05502111A (en)
DE (2) DE3930584A1 (en)
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WO (1) WO1991004153A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4134161C2 (en) * 1991-10-11 1996-12-12 Basys Gmbh Method and apparatus for treatment of printing plates
DE4241611C2 (en) * 1992-12-10 1995-11-16 Renker Gmbh & Co Kg A method for increasing the actinic opacity electrophotographic copies by means of light-sensitive diazo layers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3578444A (en) * 1968-06-13 1971-05-11 Union Carbide Corp Method of making positive-working lithographic plates by electrostatic image
US4491628A (en) * 1982-08-23 1985-01-01 International Business Machines Corporation Positive- and negative-working resist compositions with acid generating photoinitiator and polymer with acid labile groups pendant from polymer backbone
EP0262475A2 (en) * 1986-10-03 1988-04-06 M.A.N.-ROLAND Druckmaschinen Aktiengesellschaft Printing machine
DE3705439A1 (en) * 1987-02-20 1988-09-01 Man Technologie Gmbh press
EP0289056A2 (en) * 1987-05-01 1988-11-02 Fuji Photo Film Co., Ltd. Electrophotographic lithographic printing plate precursor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3578444A (en) * 1968-06-13 1971-05-11 Union Carbide Corp Method of making positive-working lithographic plates by electrostatic image
US4491628A (en) * 1982-08-23 1985-01-01 International Business Machines Corporation Positive- and negative-working resist compositions with acid generating photoinitiator and polymer with acid labile groups pendant from polymer backbone
EP0262475A2 (en) * 1986-10-03 1988-04-06 M.A.N.-ROLAND Druckmaschinen Aktiengesellschaft Printing machine
DE3705439A1 (en) * 1987-02-20 1988-09-01 Man Technologie Gmbh press
EP0289056A2 (en) * 1987-05-01 1988-11-02 Fuji Photo Film Co., Ltd. Electrophotographic lithographic printing plate precursor

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DE59010226D1 (en) 1996-04-25 grant
DK0491761T3 (en) 1996-04-15 grant
DE3930584A1 (en) 1991-03-14 application
EP0491761A1 (en) 1992-07-01 application
EP0491761B1 (en) 1996-03-20 grant
FI920474A0 (en) 1992-02-04 application
FI920474D0 (en) grant

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