CN100448689C - Method of marking a lithographic printing plate precursor - Google Patents
Method of marking a lithographic printing plate precursor Download PDFInfo
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- CN100448689C CN100448689C CNB038237113A CN03823711A CN100448689C CN 100448689 C CN100448689 C CN 100448689C CN B038237113 A CNB038237113 A CN B038237113A CN 03823711 A CN03823711 A CN 03823711A CN 100448689 C CN100448689 C CN 100448689C
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
- B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1083—Mechanical aspects of off-press plate preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/02—Cover layers; Protective layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials For Photolithography (AREA)
- Printing Plates And Materials Therefor (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A method of making a heat-sensitive lithographic printing plate s precursor is disclosed which comprises the steps of (i) providing a web of a lithographic support having a hydrophilic surface; (ii) coating a layer comprising a phenolic resin on the hydrophilic surface of the web; is (iii) drying the layer; (iv) a heating step wherein the web temperature is maintained above 150 DEG C during a period of between 0.1 and 60 seconds; (v) winding the coated web on a core or cutting the coated web into sheets. Is The short on-line heating step provides a significant improvement of the aging behavior of the precursor. A stable sensitivity is obtained shortly after coating.
Description
Technical field
The present invention relates to heat sensitive Lighographic printing plate precursor, it comprises phenolic resins.
Background technology
Typically, lithography technique comprises that the so-called stencil paper of use is as being assemblied in the galley on the direct rotary machine cylinder.Negative transmits lithographic image in its surface, by ink being coated onto described image, ink being delivered to from the negative then and receiving material (paper typically) and obtain printed matter.In the lithographic printing of routine, ink and moisture damping solution (also claiming to soak liquid) are provided to lithographic image, and lithographic image comprises the (or hydrophobic of oleophylic, promptly accept ink, repel water) regional and hydrophilic (or oleophobic, promptly accept water, repel ink) zone.In so-called anhydrous offset lithography, lithographic image comprises accepts ink and antiplastering (abhesive) ink (repulsion ink) zone, and in anhydrous offset lithography process, has only ink feed to negative.
Stencil paper exposes by image mode usually and handles the image forming material that is called plate front body and obtains.Remove known photographic plate, so-called sensitization header board is suitable for carrying out the UV contact exposure by thin barrier film, and very universal for the end in nineteen ninety to heat sensitive plate precursor.The advantage of this type of hot material is sunlight stability, especially for the direct plate-making method of so-called computer (wherein plate front body is directly exposed, and does not promptly use thin barrier film).This material is exposed under heat or the infrared ray, produces heat and cause (physics-) chemical process, for example ablation, polymerization, by not dissolving of causing of crosslinked polymer, solubilising that heat causes or the particle aggregation of thermoplasticity polymeric latex.
Though some such heat treatments can be made plate without wet-treating, the most general hot plate is to form image by the dissolubility difference that alkaline developer is caused by heat between the exposure area of coating and unexposed area.Typically, coating comprises the lipophile adhesive, phenolic resins for example, and by the imaging mode exposure, the solubility of developer is not that to reduce (negativity running) be increase (positivity running).In processing procedure, the difference of solubility causes the migration in coating non-image (non-printing) zone, thereby exposes hydrophilic carrier, and the image of coating (printing) zone is retained on the carrier.The exemplary of this type of galley is described in EP-As625728,823327,825927,864420,894622 and 901902.
The step of industrial production plate precursor comprises launches rolling mesh carrier material (it is aluminium typically), coat one or more layers on the net, come dry coating by blowing hot-air on the net, at last at the net that twines again on the axle after applying, net after perhaps will applying immediately cuts into thin slice, piles up then and packing.On commercial scale, all these steps all " online " are carried out, promptly with one way continuous operate in mobile carrying out on the net, without the storage of any centre.
The particular problem relevant with the hot plate precursor that contains phenolic resins be their sensitivity to the time instability resist developer more because coating can become gradually, thereby in the imaging mode exposure process, must apply more heat and cause the imaging course.Typically high sensitivity is (for example less than 100mJ/cm
2) just obtaining after the coating, be reduced to equilibrium valve then lentamente and be for example 250mJ/cm
2Reach the required ageing time of stable sensitivity and can after coating, spend some months.In order to shorten ageing time, WO 99/21715 has proposed by soon material is placed on the time of heat treatment one elongated segment in 40-90 ℃ the baking oven after coating, and it is 4 hours at least, and most preferably is 48 hours at least.US 6,251, and 559 suggestions are promptly heated more than the glass transition temperature of component separately under higher temperature or the of short duration processing of the dicing sheet of spaced apart is feasible.High temperature preferably is no more than 150 ℃.But, need handle a few minutes under these high temperature reaches stable sensitivity, and disclosed heat treatment method can not onlinely carry out in the prior art: since net can height to the speed of 50m/min for example through modern coating path, heat treatment is in the coating path that for example can prolong 250m in 5 minutes.Therefore, for example at US 6,251,559 and WO 99/21715 in the known processing method described can only " off-line " carry out, be about to the volume of thin slice or be stacked in the baking oven, and place the time that needs.But because several reasons must be avoided off-line storage.Except extra cost and logistic implications, clearly rolling up or pile can not be by uniform heating, because the inside of volume or heap and outside meeting are through different Temperature Distribution.Therefore, need a kind of effective methods of heating treatment that provides, this method can online implementation before wound web on the axle is maybe thinly sliced net.
Summary of the invention
One aspect of the present invention provide a kind of aging contain phenolic resins to heat sensitive printing plate material at line method.This purpose method of 1 by the following technical programs realizes, it is characterized in that dry coating is through of short duration heating steps.According to the present invention, disclosed in the prior art and can only substitute by online heating steps in the long heat treatment that off-line carries out, in second, preferred 1-30 is increased at least 150 ℃, preferably at least 170 ℃ with the temperature of net in second to online heating steps at 0.1-60.
Method of the present invention can be produced heat sensitive plate precursor, and this precursor is in two or three weeks after production rather than have stable sensitivity in the some months.Do not need extra aging, but be within the scope of the present invention obviously according to the specific embodiments of of short duration online heating steps of the present invention and extra off-line combined with heat treatment.
Specific embodiments of the present invention defines in following technical proposals.
Technical scheme of the present invention:
1, a kind of method of making heat sensitive Lighographic printing plate precursor may further comprise the steps:
(i) provide the net of the lithographic support on possess hydrophilic property surface;
(ii) on the hydrophilic surface of net, apply the coating that contains phenolic resins;
(iii) dry coating;
(iv) heating steps, wherein Wang temperature remains in second more than 150 ℃ at 1-30;
(v) precursor is wrapped in axle and upward or with precursor cuts into thin slice.
2, according to the method for technical scheme 1, wherein during heating steps, the temperature of net remains in second more than 170 ℃ at 1-30.
3, according to the method for technical scheme 1 or 2, wherein heating steps is undertaken by blow hot-air or steam on precursor.
4, according to the method for technical scheme 1 or 2, wherein heating steps by be radiated at precursor infrared or the microwave radiation under carry out.
5, according to the method for technical scheme 1 or 2, step (iv) and step (also comprise cooling step v).
6, according to the method for technical scheme 5, wherein during cooling step, the temperature of the net of precursor reduces with the average cooling rate that is higher than the precursor of preserving under environmental condition.
7, according to the method for technical scheme 6, wherein said average cooling rate is 0.5 ℃/s at least.
8, according to the method for technical scheme 5, wherein during cooling step, the temperature of net is reduced to T2 with the average cooling rate that is lower than 10 ℃/s from T1, and T1 is higher than Tg and T2 is lower than Tg, and Tg is the glass transition temperature that contains phenolic coating.
9, according to the method for technical scheme 8, wherein during cooling step, reduce the temperature of net
-be reduced to T1 in the phase I with the average cooling rate of at least 10 ℃/s;
-be reduced to T2 with the average cooling rate that is lower than 10 ℃/s from T1 in second stage
-be reduced to about environment temperature with the average cooling rate of at least 10 ℃/s from T2 in the phase III.
10, according to the method for technical scheme 8 or 9, wherein T1 is that Tg+20 ℃ and T2 are Tg-20 ℃.
Description of drawings
Fig. 1 has shown during making the method for optimizing to heat sensitive Lighographic printing plate precursor of the present invention, the Temperature Distribution of net.
Fig. 2 has shown the schematic representation of apparatus of carrying out the suitable embodiment of the inventive method.
The specific embodiment
The coating that contains phenolic resins on hydrophilic carrier and the carrier that heat sensitive Lighographic printing plate precursor is comprised of the present invention.Coating can be made up of one or more layers following embodiment.Phenolic resins can be present in one or more layers of described coating.
The temperature reference of carrier and coating is regarded in any reference to precursor temperature of this paper as: coating is very thin usually, and about one or several microns, and the common thickness of carrier is between the 0.1-0.5 millimeter; Therefore carrier is preferably metallic carrier, as big radiator to coating, and the temperature of coating equals or is in close proximity to the temperature of carrier, no matter whether by heat or cold heating or the cooling step that carries out this paper discussion to the coated side or the back side of precursor are provided, perhaps the two all carries out.In fact, the temperature value of this paper report is by the thermocouple assembly record attached to the net back side, and when net passed through all parts of coating apparatus, this device can remotely be read temperature value.Like this, can note the inventive method the precise temperature profile in steps.Unless specifically defined otherwise, all temperature of this paper report all are the net temperature that obtains from described thermocouple.For above-mentioned reasons, the temperature value that should clearly net of those skilled in the art is substantially equal to the temperature of online dry coating.
Any coating process can be used for applying one or more coating solutions to the hydrophilic surface of carrier.Laminated coating can or once apply several coating solutions simultaneously by each layer of coating/drying sequentially and apply.Typically, carry out drying by blow hot-air on coating, the temperature of hot-air is 80-150 ℃ suitably at least at 70 ℃ usually, and especially at 90-140 ℃.Also have other thermal source, for example infrared lamp or microwave radiation also can be used for drying steps.Be generally 15-600 second drying time.But in drying steps, remove all solvents optional (and being impossible).Even residual solvent composition can be counted as extra component variable, relies on it can be with coating ingredients optimization.Therefore herein the drying steps concluding time of regulation be coating become self-supporting and touch dry in.
After finishing, drying steps begins heating steps, preferred dry carrying out immediately afterwards.Perhaps, precursor is cooled off between drying and heating steps earlier, but this is optional.During heating steps, to heat supply on the dry coating, so that the temperature of coating remains on the level (temperature of surrounding air is defined as 20 ℃ at this paper) that is higher than the precursor of preserving under the environment temperature.So temperature the when temperature during heating steps can be lower than the drying steps end.More preferably, remain on coating temperature when being higher than drying steps and finishing in the temperature of heating steps floating coat.Between the online period of heating, the net temperature of precursor in time second, more preferably is elevated at least 150 ℃ at 1-30 at 0.1-60 in second, preferably at least 170 ℃.During heating steps, the net temperature upper limit is defined by temperature threshold, and temperature threshold is that initiation coating imaging course is necessary.Therefore the described upper limit depends on the concrete component of coating, but usually at about 200 ℃ or more preferably at about 250 ℃.Heating can cause irreversible chemistry or physical change take place in the coating under higher temperature, makes precursor be unsuitable for the image record.
Heating can be by for example blowing hot-air and/or steam on Lighographic printing plate precursor, with infrared ray or microwave radiation precursor, or carry out with the cylinder contact precursor of heating.The combination of these methods also is fit to.The temperature of hot-air and/or steam is higher than 150 ℃, preferably at least 170 ℃.The back side of available infrared radiation coating, carrier or the two.If use the infrared radiation coating, then ultrared wavelength and/or intensity can not cause the imaging course of coating.Also can be with the cylinder of heating, the back side of preferred thermostatically controlled heated roller contact coating, carrier or the two, the preferred back side.Cylinder is metal roller preferably.
After the heating steps, preferably precursor is cooled off before the thin slice twining on the axle or cut into independently.Perhaps, after heating steps, immediately net is twined or cuts into thin slice on axle, then cooling.Preferred cooling step is a cooling step quick, " initiatively ", promptly to reduce the temperature of coating than the cooling velocity of the preceding height of preserving under the room temperature.In embodiment preferred discussed further below, cooling step is a multistage process, and wherein initiatively cooling can be interrupted by " passive " cooling stage, typically near the transformation of the temperature interval the coated glass conversion temperature.Be meant net is less than or equal to the cooling step that cools off at average cooling rate under the cooling velocity of the precursor of preserving under the environmental condition by " passive " cooling.
Average cooling rate during cooling step or cooling stage is defined as the ratio of cooling step or stage temperature difference when beginning and finishing and in the time-continuing process in described cooling step or stage.
Initiatively cooling can realize by the whole bag of tricks, for example, contacts with one or more cylinders (preferable alloy cylinder) by precursor, so that the heat of precursor is delivered on the cylinder apace.Certainly other cooling means also is feasible, for example, and blow air on precursor.Yet preferably use the metal chilling roll, because closely contact between chilling roll and the precursor, it is fast that the precursor that makes the temperature ratio be kept at (promptly not contact with chilling roll) under the environmental condition descends, and also can cool off even the temperature of chilling roll remains on the numerical value that is higher than surrounding air.Initiatively cooling can be by for example realizing at the precursor of 50-120 ℃ metal chilling roll contact just end heating steps with temperature.Chilling roll is made up of other material, for example, can use the perhaps material of heat conductivity of low-heat.But the back side of chilling roll contact net or coat side, or the two.Obviously, if the temperature difference between chilling roll and the precursor is higher, then can obtain cooling effect faster.The minimum of a value of preferred average cooling rate is 0.5 ℃/s, more preferably 1 ℃/s, even more preferably 3 ℃/s.
In some embodiments, avoid very high average cooling rate, for example be higher than 30 ℃/s,, can reduce or eliminate fully the beneficial effect of heating steps because when cooling takes place very soon.Therefore, this reason may relate to the amorphous state of high-load, if phenolic resins is quickly cooled to below its glass transition temperature (Tg)." Tg " is meant the glass transition temperature of the phenolic resins in the component at this paper, and coated, the dry and heating of described component promptly contains the glass transition temperature of the coating of phenolic resins.Described Tg value can be measured fast by known calorimetry.If contain the phenolic resins of a large amount of amorphous states in the coating, be transformed into more crystalline states inevitably in then can be after coating several days or a few week, can illustrate that then the sensitivity that can be observed towards lower moves during material aging.For this effect is minimized, the maximum of restriction average cooling rate is useful, for example less than 30 ℃/s, is more preferably less than 20 ℃/s, and most preferably less than 10 ℃/s.
On the other hand, consider high-speed, preferably of short duration, the fast cooling step of net through modern coating apparatus.Best compromise scheme between the requirement that opposes on these surfaces can realize by three following stage cooling steps:
-cooling stage 1: cooling makes the temperature of precursor drop to T1 fast, and it is higher than the Tg of phenolic resins.
-cooling stage 2: slowly cooling makes the temperature of precursor drop to the T2 that is lower than Tg.
-cooling stage 3: be cooled fast to about environment temperature once more.
The first quick cooling stage can comprise very high average cooling rate, for example at least 10 ℃/s, and more preferably 10-20 ℃/s, even more preferably greater than 20 ℃/s.In second cooling stage, near the transformation of the temperature interval Tg is carried out with low average cooling rate, and promptly the net temperature of precursor in the interval of T2, (as is lower than 10 ℃/s) reduction with the average cooling rate that is lower than in the stage 1 at T1.Preferred T1 and T2 value are respectively Tg+20 ℃ and Tg-20 ℃, more preferably are respectively Tg+10 ℃ and Tg-10 ℃.According to the embodiment that is more preferably, in the stage 1, cool off temperature up to precursor fast just more than the Tg at phenolic resins, slowly cool off to just being lower than Tg from just being higher than Tg then, under the situation that ageing properties is not produced appreciable impact, can carry out another quick cooling stage at last.Scope between " just being higher than " used herein and " just being lower than " Tg is for example from Tg+5 ℃ to Tg-5 ℃ scope, more preferably from Tg+2 ℃ to Tg-2 ℃ scope.
Average cooling rate at second cooling stage can higher or be lower than with respect to the cooling velocity under the environmental condition, does not promptly use the cooling velocity of cooling means (for example cylinder).The scope of preferred average cooling rate is from 0.1 ℃/s to 5 ℃/s in second cooling stage, more preferably 0.2 ℃/s to 3 ℃/s; Value between 1 ℃/s and 2 ℃/s can produce superior results.In case the temperature of net descends up to being lower than Tg, then can cool off fast once more at the 3rd cooling stage, for example average cooling rate is at least 10 ℃/s, more preferably 10-20 ℃/s or even greater than 20 ℃/s.
The typical Tg of phenolic resins (for example commercial novolaks that get) is between 75-95 ℃, more typically between 80-90 ℃.The present invention preferably exemplary of net Temperature Distribution shows that in Fig. 1 wherein the Tg of phenolic resins is 84 ℃.In Fig. 1, be that to carry out drying and temperature be that 160 ℃ hot-air is used for heating steps for 130 ℃ hot-air with temperature.During first cooling stage, in seconds drop to 100 ℃ and realize quick cooling from＞150 ℃, in 16 seconds, slowly cool off then from 100 ℃ to 70 ℃ (be average cooling rate be 1.9 ℃/s), in seconds cool off fast once more at last to reach about environment temperature.
The material that above-mentioned heating and cooling step provides is characterised in that the stable sensitivity after the ageing process, and ageing process obviously shortens than the material without these steps, and for example, two or three week is than some months.Except improved ageing properties, the resistance that coating of materials according to the invention also demonstrates mechanical damage significantly improves.More particularly, having improved the friction resistance greatly by above-mentioned cooling procedure, is slow process near Tg at interval wherein.Method of the present invention can be implemented with coating apparatus, and its typical example provides in Fig. 2.Carrier 1 launches from rolling up 2, coats one or more layers with coater 3 then, and is subsequently that coating is dry in many parts drier 4-5-6-7, by thermal source 8 heat treated, thermal source is an infrared source or blow the nozzle of hot-air for example, by cylinder 9 coolings, winds up on axle 13 at last then.Air nozzle 10-11-12 can be used for other cooling: cylinder 9 preferably remains on the temperature of the Tg that just has been higher than phenolic resins, and the temperature of nozzle 10 just has been lower than Tg, so that near the transformation of the temperature interval the Tg is slow.
By plate front body of the present invention form lithographic image be since during handling one or more layers coating in developer by thermoinducible dissolubility difference.Typically, change the developer solubility of the layer that contains phenolic resins by exposure.One or more layers extra play helps imaging process.In some embodiments, coating can further contain the layer that is unfavorable for the imaging course, for example, and the layer that solubility does not change basically to exposure in developer.One of them example is a protective layer, and protective layer all dissolves in developer on the top of coating and in exposure and unexposed area.Layer between carrier and imaging layer is inoperative to imaging process usually.
Solubility difference between the image of lithographic image (printing, lipophile) and non-image (non-printing, hydrophily) zone is characterised in that dynamic action rather than thermodynamics effect, and promptly non-image areas is characterised in that than image-region and dissolves in developer fast.In the most preferred embodiment, before the image-region chemically reactive, non-image areas is dissolving fully in developer, so image-region is characterised in that the ink acceptance of tangible edge and height.Preferably finish and the time difference of image-region between beginning to dissolve is to surpass 10 seconds, more preferably surpass 20 seconds, and most preferably surpass 60 seconds, thereby wide video picture scope is provided in non-image areas dissolving.
According to an embodiment, plate precursor is the negativity running, and promptly image-region is corresponding to the exposure area.Suitable negativity running coating comprises phenolic resins and latent property Bronsted acid, and the property Bronsted acid of diving can produce acid when heating or IR radiation.These acid catalysis coatings are crosslinked in the post-exposure heating steps, thus the sclerosis exposed areas.Therefore, unexposed area can be used the developer flush away, to expose following hydrophillic bottom layer.For the such negativity of more detailed description running galley, we are with reference to US 6,255, and 042 and US 6,063,544 and as a reference with these files.
According to another embodiment, galley is the positivity running.In this embodiment, one or more layers of coating can be by the thermal induction solubilising, and promptly they are resisted developer and accept ink at unexposed state, and becoming when irradiation heat and infrared ray dissolves in developer, thereby manifests the hydrophilic surface of carrier.So after exposure and video picture, remove the exposure area from the hydrophily of carrier and definition non-image (non-printing) zone, and do not remove unexposed area from lipophile image (printing) zone of carrier and definition.
The carrier possess hydrophilic property of Lighographic printing plate precursor surface or hydrophilic layer is provided.Carrier can be a for example plate of flaky material, or circle tube element sleeve pipe for example, and it can slide around the print drum of printing machine.Preferably, carrier is a metallic carrier, for example aluminium or stainless steel.Carrier also can be the laminated material that contains aluminium foil and plastic layer (as polyester film).
Particularly preferred lithographic support is that electrochemistry makes shaggy and anodized aluminum support.Aluminium rough surface and anodization are known in the art.Anodised alumina supporter can improve its surperficial hydrophilic nmature through handling.For example, alumina supporter can be a silicate, and (for example 95 ℃) handle the surface of alumina supporter with sodium silicate solution by at high temperature.Perhaps, phosphoric acid salt is handled, and comprising handling alumina surface with phosphoric acid solution, phosphoric acid solution can further contain inorganic fluoride.In addition, alumina surface can clean with citric acid or citric acid solution.This processing can at room temperature be carried out or carry out under slightly high temperature (for example about 30-50 ℃).Further interested processing comprises with bicarbonate solution cleans alumina surface.Further, the sulfuric ester of available polyethylene phosphonic acids, polyethylene methylphosphonic acid, polyethylene alcohol phosphate, polyvinyl sulfonic acid, polyethylene benzene sulfonic acid, polyvinyl alcohol and handle by the polyvinyl alcohol acetal that forms with the reaction of the fatty aldehyde of sulfonation.Clearly, one or more such post processings can be separately or in conjunction with carrying out.Being described in greater detail among GB-A-1 084 070, DE-A-4 423 140, DE-A-4 417 907, EP-A-659 909, EP-A-537633, DE-A-4 001 466, EP-A-292 801, EP-A-291 760 and the US-P-4 458005 of these processing provides.
According to another specific embodiments, carrier can be a flexible carrier also, and it has hydrophilic layer, below is called " basic unit ".Flexible carrier is for example paper, plastic foil, flake aluminum or its laminated material.The example of preferred plastic foil is polyethylene terephthalate film, poly-naphthalene methylene acid second diester film, CAM, polystyrene film, polycarbonate membrane etc.Plastic film support can be opaque or transparent.Basic unit is preferably by the curing agent crosslinked crosslinked hydrophilic layer of hydrophilic adhesive with for example tetraalkyl original silica ester of formaldehyde, glyoxal, PIC or hydrolysis.The object lesson that is used for suitable hydrophily basic unit of the present invention is open at EP-A-601 240, GB-P-1 419 512, FR-P-2 300 354, US-P-3 971 660 and US-P-4 284705.
Phenolic resins preferably has the adhesive of pKa less than 13 acidic-group, dissolves in the water-based alkaline developer or swelling at least to guarantee it.Advantageously, adhesive is polymer or the condensation polymer with free phenolic hydroxyl group, can obtain by for example phenol, resorcinol, cresols, xylenols or pseudocuminol and aldehyde (especially formaldehyde) or reactive ketone.Polymer can be extra contain other monomer, these monomers do not have acid unit.This type of unit comprises vinyl aromatic compounds, methyl (methyl) acrylate, phenyl (methyl) acrylate, benzyl (methyl) acrylate, Methacrylamide or acrylonitrile.In preferred specific embodiments, phenolic resins is novolaks, resol or polyvinylphenol.Novolaks are cresol/formaldehyde or cresols/xylenols/formaldehyde novolac preferably, and advantageously the amount of novolaks is that gross weight based on all adhesives is at least 50% by weight, preferably is at least 80% by weight.Advantageously, the amount of phenolic resins is to be 40-99.8% by weight based on the gross weight of nonvolatile element in the coating under every kind of situation, preferably is 70-99.4% by weight, especially preferably is 80-99% by weight.
The solubility property of phenolic resins in developer can be regulated component by optional solubility and finely tune.More specifically, can use video picture accelerator and video picture inhibitor.These compositions addings can be contained the layer of phenolic resins and/or other layer of coating.
The video picture accelerator is the compound as dissolution accelerator, because they can increase the dissolution velocity of phenolic resins.For example, cyclic acid anhydride, phenol or organic acid can be used for improving the visualization capabilities of water.The example of cyclic acid anhydride comprises phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-bridging oxygen-4-tetrahydrochysene-phthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, maleic anhydride, chloromaleic acid acid anhydride, α-phenyl maleic anhydride, succinyl oxide and PMA acid anhydrides, as U.S. Patent No. 4, described in 115,128.The example of phenol comprises bisphenol-A, p-nitrophenol, p-thanatol, 2,4,4 '-trihydroxybenzophenone, 2,3,4-trihydroxy-benzophenone, 4-dihydroxy benaophenonel, 4,4 ', 4 " trihydroxy-triphenyl methane and 4; 4 '; 3 ", 4 " and tetrahydroxy-3,5; 3 ', 5 '-tetramethyl triphenyl-methane etc.The organic acid example comprises sulfonic acid, sulfinic acid, alkylsurfuric acid, phosphonic acids, phosphate and carboxylic acid, as for example JP-A-60-88, and 942 and 2-96, described in 755.These organic acid object lessons comprise p-toluenesulfonic acid, DBSA, p-toluenesulfinic acid, ethyl sulfuric acid, phenyl-phosphonic acid, phenyl phosphinic acid, phosphoric acid one phenyl ester, phosphate diphenyl ester, benzoic acid, M-phthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 3,4,5-trimethoxy cinnamic acid, phthalic acid, terephthalic acid (TPA), 4-cyclohexene-1,2-dicarboxylic acids, erucic acid, laurate, n-undecanoic acid and ascorbic acid.Cyclic acid anhydride, phenol or organic acid amount contained in the coating are preferably by weight in the 0.05-20% scope.
In preferred embodiments, coating also contains colour developing opposing agent, is also referred to as the colour developing inhibitor, promptly can postpone one or more compositions of unexposed area dissolving in processing.The effect of dissolution inhibitor preferably reduces by heating, so that the dissolving of exposure area do not postpone, thereby and can obtain huge dissolving difference between exposure area and the unexposed area.Other layer that this type of video picture opposing agent can be added the layer that contains phenolic resins or adds material.
The compound of describing at for example EP-A 823 327 and WO97/39894 can be used as dissolution inhibitor, owing to for example pass through the interaction of hydrogen bridge structure and coating neutral and alkali dissolved adhesive.The inhibitor of this type typically contains hydrogen bridge and forms group, and for example (CO-), sulfinyl (SO-) or sulfonyl (SO for nitrogen-atoms, group, carbonyl
2-) and big hydrophobic part, for example one or more aromatic protons.
Other suitable inhibitor can improve the developer repellence, because they can postpone alkaline developer solution to the layer infiltration that contains phenolic resins.This compounds can be present in layer itself, described in EP-A 950 518, or is present in the development barrier on described layer top, described in EP-A864 420, EP-A 950 517, WO 99/21725 and WO 01/45958.In the embodiment of positivity running, preferably containing in the barrier layer can not be by the polymeric material of developer dissolves or infiltration, for example acrylic acid (being total to) polymer, polystyrene, styrene-propene acid copolymer, polyester, polyamide, polyureas, polyurethane, NC Nitroncellulose, epoxy resin and silicones.In this embodiment, solubility or the developer of barrier layer in developer can be by shining heat or infrared ray increases to the permeability on barrier layer.
The preferred example of the one type of inhibitor in back comprises waterproof polymer, for example contains the polymer of siloxanes and/or perfluoroalkyl unit.In typical specific embodiments, precursor contains the barrier layer, and this layer comprises waterproof polymer, and suitable amount is 0.5-25mg/m
2, preferred 0.5-15mg/m
2, 0.5-10mg/m most preferably
2According to the hydrophobic/fuel shedding quality of compound, Lve Gao or lower slightly amount also are suitable.When waterproof polymer also repelled ink, for example the amount of polysiloxanes was higher than 25mg/m
2Situation under can cause the low ink acceptance of unexposed area.On the other hand, content is lower than 0.5mg/m
2Can cause video picture resistance unsatisfactory.Polysiloxanes can be wire, ring-type or complex cross-linked polymer or copolymer.The term polysiloxane compound should comprise any compound that contains more than a siloxy group-Si (R, R ')-O-, and wherein R and R ' are optional substituted alkyl or aryls.Preferred siloxanes is phenylalkyl siloxanes and dialkylsiloxane.The quantity of siloxy group is 2 at least in (being total to) polymer, preferably is at least 10, more preferably is at least 20.Can be less than 100, preferably less than 60.In another embodiment, waterproof polymer is poly-(oxyalkylene) and contain siloxanes and/or the block copolymer of the polymer of perfluoroalkyl unit or graft copolymer.Suitable copolymers contains about 15-25 siloxane unit and 50-70 oxyalkylene group.Preferred example comprises the copolymer that contains phenyl methyl siloxanes and/or dimethyl siloxane and oxirane and/or expoxy propane, for example Tego Glide 410, Tego Wet 265, Tego Protect5001 or Silikophen P50/X, these all can be from German Tego Chemie, and Essen buys.This analog copolymer as surfactant, because its bifunctional structure, even when using as the composition of the solution identical with phenolic resins, also tends to the interface that will self be placed between coating and air, thereby forms independently top layer on coating.
Simultaneously, this type of surfactant can improve the quality of coating as the smears.Perhaps, can be coated in second solution that contains phenolic resins layer top being applied at waterproof polymer.In this specific embodiments, can advantageously use the solvent in second coating solution, second coating solution can not dissolve the composition that is present in the ground floor, thereby obtains the anti-water of high concentration on the top of material.
Coating preferably also contains the compound that absorbs infrared ray and the energy that absorbs is changed into heat.The IR absorption compound can be present in identical with phenolic resins layer, above-mentioned optional barrier layer or optional other layer.According to highly preferred embodiment, dyestuff or pigment are concentrated in or near the barrier layer, for example among the intermediate layer between oleophilic layer and barrier layer.According to this embodiment, the amount of IR absorption compound is higher than the amount of IR absorption compound in oleophilic layer or the barrier layer in the described intermediate layer.The concentration of IR absorption compound is typically between 0.25-10.0wt.%, more preferably between 0.5-7.5wt.% in the coating.Preferred IR absorption compound is a dyestuff, for example cyanine and merocyanine dye or pigment carbon black for example.The example of suitable IR absorbent is described in for example EP-A-823327,978376,1029667,1053868,1093934; Among the WO97/39894 and 00/29214.Preferred compound is following cyanine dye:
For the surface of protective finish, especially, can also randomly use protective layer from mechanically infringement.Protective layer contains at least a water-soluble polymeric binder usually; the for example polyvinyl acetate of polyvinyl alcohol, polyvinylpyrrolidone, partial hydrolysis, gelatin, carbohydrate or hydroxyethylcellulose; and available any known method production; for example can produce from the aqueous solution or dispersion; if desired; can contain a small amount of organic solvent, for example contain, by weight less than 5% organic solvent based on protective layer used coating solvent gross weight.The thickness of protective layer can be suitable for any amount, advantageously mostly is most 5.0 μ m, preferred 0.1-3.0 μ m, preferred especially 0.15-1.0 μ m.
Randomly, contain the coating of phenolic resins and one or more layers can further contain supplementary element more specifically.Preferred composition is an additional binder for example, especially comprises the polymer of sulfanilamide (SN) and phthalimide-based group, to improve the cycle of operation and the chemoresistance of plate.The example of this base polymer is described in EP-A 933682, EP-A 894622 and WO 99/63407.Can also add colouring agent, the dyestuff or the pigment of visible color for example is provided to coating, they are retained in the coating of exposure area, so that produce visible image in exposure with after handling.The exemplary of this type of contrast dyestuff be amino replace three-or triarylmethane colouring matters, for example crystal violet, crystal violet, Victoria's ethereal blue, flexoblau 630, basonylblau 640, auramine and peacock green.
Preparation for Lighographic printing plate precursor, any known method can be used, for example, mentioned component solvent mixture can be dissolved in, irreversible reaction takes place in solvent mixture discord composition, and preferably formulates planned painting method, coating layer thickness, coating composition and drying condition.Suitable solvent comprises ketone, for example methyl ethyl ketone (butanone), and chlorinated hydrocabon, trichloro-ethylene or 1,1 for example, the 1-trichloroethanes, alcohols, for example methyl alcohol, ethanol or propyl alcohol, ethers, for example oxolane, ethylene glycol-monoalky lether, ethylene glycol monoalkyl ether for example, as 2-methoxyl group-1-propyl alcohol or propylene-glycol monoalky lether and ester, for example butyl acetate or propylene-glycol monoalky lether acetic acid esters.Can also use the mixture of specific purposes, can be extra contain solvent, for example acetonitrile, diox, dimethylacetylamide, methyl-sulfoxide or water.
Terminal temperature difference can adopt image mode irradiation Lighographic printing plate precursor, can directly use thermal exposure, the mode by thermal head for example, or indirectly by infrared ray, preferably near infrared ray.Preferably, by above-mentioned IR line absorption compound infrared ray is changed into heat.Of the present invention preferably insensitive to visible light to heat sensitive Lighographic printing plate precursor, promptly can not work basically to the dissolution velocity of coating in developer by the irradiation visible light.Most preferably, coating is insensitive to the daylight of environment, and promptly the intensity of visible light (400-750nm) and nearly UV line (300-400nm) and irradiation time are corresponding to normal condition of work, so material can be handled material under the environment that does not need safe light.Should refer to be radiated to daylight " insensitive " and can not cause basically under the environment daylight that the dissolution velocity of coating in developer changes.In the embodiment of preferred daylight stable, do not comprise photographic composition in the coating, for example (quinone) two trinitride (diazide) or diazonium (nium) compound, light acid, photoinitiator, sensitizer etc., they can absorb nearly UV and/or visible light in sunlight or the office lights, thereby change the solubility of exposure area floating coat.
Plate precursor of the present invention can be shone infrared ray by the mode of for example LEDs or laser instrument.Most preferably, the light that is used to shine is the wavelength that emitted by laser instrument at the approximately infrared ray of 750-1500nm, for example semiconductor laser diode, Nd:YAG or Nd:YLF laser instrument.Required laser intensity depends on the sensitivity of image recording layer, the pixel duty time of laser beam, it can be measured (typically by spot diameter, the numerical value of the modern plate when maximum intensity is 1/e2-be provided with device (plate-setter) is 10-25 μ m), the resolution ratio of sweep speed and exposure sources (be the quantity that can set pixel in each air line distance unit, usually with per inch count or dpi represents; Typical value is 1000-4000dpi).
The general laser irradiating device that uses two types: interior drum (ITD) and external drum (drum) be plate-be provided with device (XTD).The characteristic feature that is used for the I TD plate adjuster of hot plate is the laser intensity up to several watts of the very high sweep speed of 500m/sec and needs.The XTD plate adjuster that is used for hot plate is in low sweep speed, and for example the 0.1-10m/sec operation has the typical laser intensity of about 200mW to about 1W down.
Known plate adjuster can be used as (off-press) exposure sources of disembarking, and its advantage has been to reduce the downtime of printing.XTD plate governor arrangements also is used in machine (on-press) exposure, and its advantage is directly to write down (immediateregistration) in polychrome printing.At for example US 5,174,205 and US 5,163,368 have description in more ins and outs of machine exposure sources.
In development step, the non-image areas of coating is removed by soaking in the alkaline developer solution of routine, can combine with mechanical friction, for example passes through rotary brush.During video picture, can also remove the water soluble protective layer of any existence.The ratio of preferred silica and alkali metal oxide is at least 1 silicate-base developer, is not damaged with the alumina layer (if existence) of guaranteeing bottom.Preferred alkali metal oxide comprises Na
2O and K
2O with and composition thereof.Except alkali silicate, developer can randomly contain more component, buffer substance for example commonly known in the art, complexant, antifoam, a small amount of organic solvent, anticorrisive agent, dyestuff, surfactant and/or hydrotropic solvent.Preferred temperature under 20-40 ℃ in processing unit automatically the convention according to prior art develop the color.For regeneration, can use the alkali metal silicate solutions of alkali metal content aptly as 0.6-2.0mol/l.These solution can have the silica/alkali metal oxide ratio identical with developer (but normally lower), and can randomly contain more additive equally.The demand of regrown material must be special regulations such as the day productivity ratio, image area of used display device, plate, and being generally every square metre of recording materials has 1-50ml.Can regulate addition, for example pass through the mensuration electrical conductivity as what describe among the EP-A 0 556 690.
If desired, plate front body according to the present invention can be carried out post processing with suitable correction agent commonly known in the art or anticorrisive agent subsequently.The repellence of the galley of finishing for raising, thus the print run time prolonged, layer can be heated to tout court high temperature (" curing ").As a result, also can improve galley to washing away the resistance of agent, correction agent and ultraviolet curable (UV-curable) printing ink.This type of hot post processing has description in DE-A 1447963 and GB-A 1154749.
Except the post processing of mentioning, the processing of plate front body also comprises cleaning step, drying steps and/or gluing step.
The galley of Huo Deing can be used for conventional, so-called wet adherography printing like this, and its ink inside and the supply of the wetting liquid aqueous solution are onboard.The so-called single liquid ink that does not have wetting liquid is used in another suitable printing process.The single liquid ink that is applicable to method of the present invention has been described in US 4,045, and 232, US 4,981,517 and US 6,140,392.In the most preferred embodiment, the single liquid ink contains the ink phase, is also referred to as hydrophobic or the oleophylic phase, with polyalcohol described in WO00/32705 mutually.
Embodiment
Following composition is coated in routine makes the online of rough surface and anodised alumina supporter, wet-process coating thickness is that 26 μ m and speed are 16m/min:
-methoxypropanol (Dowanol PM
TM) 410.80g
-methyl ethyl ketone 266.03g
-oxolane 209.20g
-40.4wt.% novolaks
Dowanol PM
TMSolution (Alnovol SPN 452
TM) 103.25g
-3,4,5-trimethoxy cinnamic acid 5.34g
-dyestuff IR-1 (shown in following formula) 2.10g
-Basonylblau 640
TM(contrast dye) 0.53g
-TEGO?Glide?265
TM
(10wt.% polyalkylene oxide/polysiloxane surfactant solution) 0.85g
-TEGO?Glide?410
TM
(10wt.% polyalkylene oxide/polysiloxane surfactant solution) 2.12g
With temperature is 135 ℃ air dry coating, passes through the heating and cooling step then.During heating steps, the air that will have temperature shown in the table 1 in 1.2 seconds blows on the coating.In comparing embodiment 1, cut off hot air nozzle.Metal chilling roll immediately that the back side and the temperature of net is as shown in table 1 afterwards contacts.Make very fast (＞30 ℃/s) be reduced to below the Tg of the temperature of heating coating with 57 ℃ chilling rolls.With 75 ℃ chilling roll, with near the temperature interval the lower speed process Tg.
Then material is gone up with different-energy density at Creo Trendsetter 3244 (830nm) and be arranged to picture.Exposed plate speed with 0.84m/min on Agfa Autolith PN85 processor uses Agfa Ozasol EP26 developer to handle down at 25 ℃, uses AgfaOzasol RC795 gluing at last.Regulation I R-sensitivity is for obtaining the required minimum energy density of 50% absorbing amount, and 50% absorbing amount has the speckle regions (200lpi) of 50% screen for to measure on colour plate in the wavelength maximum of dyestuff in the exposure area.The sensitivity of the material of in several days, measuring freshly prepd material and under environmental condition, wearing out, as shown in table 1.
Table 1
The material that data in the table 1 show according to the present invention heating 15 days after coating reach stable sensitivity, and the sensitivity of the contrast material among the embodiment 1 still changed after 25 days, find that after coating about 2 months are stabilized in 165mJ/cm
2
With the sample of embodiment 4 and 5 respectively according to description coating, drying and the cooling of the foregoing description 1 and 2, condition is that coating is shone in the IR radiation (lamps of two 12kW) of using that the hot air processing among the embodiment 2 replaces with among the embodiment 5, thereby makes the temperature of net be elevated to 150 ℃ in 2.8.The temperature of comparative example's 4 this moment (cutting off the IR lamp) net is 60 ℃.Table 2 shows and shows that embodiment 5 compares with embodiment 4, demonstrates the ageing properties that highly improves.
Table 2
Claims (10)
1, a kind of method of making heat sensitive Lighographic printing plate precursor may further comprise the steps:
(i) provide the net of the lithographic support on possess hydrophilic property surface;
(ii) on the hydrophilic surface of net, apply the coating that contains phenolic resins;
(iii) dry coating;
(iv) heating steps, wherein Wang temperature remains in second more than 150 ℃ at 1-30;
(v) precursor is wrapped in axle and upward or with precursor cuts into thin slice.
2, according to the process of claim 1 wherein that during heating steps the temperature of net remains in second more than 170 ℃ at 1-30.
3, according to the method for claim 1 or 2, wherein heating steps is undertaken by blow hot-air or steam on precursor.
4, according to the method for claim 1 or 2, wherein heating steps by be radiated at precursor infrared or the microwave radiation under carry out.
5, according to the method for claim 1 or 2, step (iv) and step (also comprise cooling step v).
6, according to the method for claim 5, wherein during cooling step, the temperature of the net of precursor reduces with the average cooling rate that is higher than the precursor of preserving under environmental condition.
7, according to the method for claim 6, wherein said average cooling rate is 0.5 ℃/s at least.
8, according to the method for claim 5, wherein during cooling step, the temperature of net is reduced to T2 with the average cooling rate that is lower than 10 ℃/s from T1, and T1 is higher than Tg and T2 is lower than Tg, and Tg is the glass transition temperature that contains phenolic coating.
9, method according to Claim 8 wherein during cooling step, reduces the temperature of net
-be reduced to T1 in the phase I with the average cooling rate of at least 10 ℃/s;
-be reduced to T2 with the average cooling rate that is lower than 10 ℃/s from T1 in second stage
-be reduced to about environment temperature with the average cooling rate of at least 10 ℃/s from T2 in the phase III.
10, according to Claim 8 or 9 method, wherein T1 is that Tg+20 ℃ and T2 are Tg-20 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02102413.8 | 2002-10-04 | ||
| EP02102413 | 2002-10-04 | ||
| US60/419,988 | 2002-10-21 |
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|---|---|
| CN1688450A CN1688450A (en) | 2005-10-26 |
| CN100448689C true CN100448689C (en) | 2009-01-07 |
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| CNB038237113A Expired - Fee Related CN100448689C (en) | 2002-10-04 | 2003-09-12 | Method of marking a lithographic printing plate precursor |
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| Country | Link |
|---|---|
| EP (1) | EP1558447B1 (en) |
| JP (1) | JP2006501505A (en) |
| CN (1) | CN100448689C (en) |
| AU (1) | AU2003299180A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060234161A1 (en) | 2002-10-04 | 2006-10-19 | Eric Verschueren | Method of making a lithographic printing plate precursor |
| EP1605309A1 (en) * | 2004-06-10 | 2005-12-14 | Degraf S.P.A. | Method and apparatus for the drying of the printing plates for flexography |
| JP4732108B2 (en) * | 2005-10-06 | 2011-07-27 | 富士フイルム株式会社 | Planographic printing plate manufacturing method |
| DE602006009919D1 (en) | 2006-08-03 | 2009-12-03 | Agfa Graphics Nv | Lithographic printing plate support |
| JP4954758B2 (en) * | 2007-03-19 | 2012-06-20 | 新日本製鐵株式会社 | Method for producing plated steel sheet with excellent corrosion resistance and paint adhesion |
| EP2065211B1 (en) | 2007-11-30 | 2010-05-26 | Agfa Graphics N.V. | A method for treating a lithographic printing plate |
| EP2098376B1 (en) | 2008-03-04 | 2013-09-18 | Agfa Graphics N.V. | A method for making a lithographic printing plate support |
| EP2106924B1 (en) | 2008-03-31 | 2011-06-29 | Agfa Graphics N.V. | A method for treating a lithographic printing plate |
| EP2263874B1 (en) | 2009-06-18 | 2012-04-18 | Agfa Graphics N.V. | A lithographic printing plate precursor |
| EP2329951B1 (en) | 2009-12-04 | 2012-06-20 | AGFA Graphics NV | A lithographic printing plate precursor |
| EP2668039B1 (en) | 2011-01-25 | 2015-06-03 | AGFA Graphics NV | A lithographic printing plate precursor |
| EP2489512B1 (en) | 2011-02-18 | 2013-08-28 | Agfa Graphics N.V. | A lithographic printing plate precursor |
| ES2642967T3 (en) | 2013-01-01 | 2017-11-20 | Agfa Graphics Nv | Copolymers (ethylene, vinyl acetal) and lithographic printing plate precursors that include such copolymers |
| EP2933278B1 (en) | 2014-04-17 | 2018-08-22 | Agfa Nv | (Ethylene, vinyl acetal) copolymers and their use in lithographic printing plate precursors |
| EP2944657B1 (en) | 2014-05-15 | 2017-01-11 | Agfa Graphics Nv | (Ethylene, Vinyl Acetal) Copolymers and Their Use In Lithographic Printing Plate Precursors |
| EP2955198B8 (en) | 2014-06-13 | 2018-01-03 | Agfa Nv | Ethylene/vinyl acetal-copolymers and their use in lithographic printing plate precursors |
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| EP3637188A1 (en) | 2018-10-08 | 2020-04-15 | Agfa Nv | An effervescent developer precursor for processing a lithographic printing plate precursor |
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| WO2021193423A1 (en) * | 2020-03-23 | 2021-09-30 | 東レ株式会社 | Cylindrical printing plate and method for manufacturing printed matter |
| EP4239411A1 (en) | 2022-03-04 | 2023-09-06 | Eco3 Bv | Method and apparatus for processing a lithographic printing plate precursor |
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2003
- 2003-09-12 CN CNB038237113A patent/CN100448689C/en not_active Expired - Fee Related
- 2003-09-12 WO PCT/EP2003/050621 patent/WO2004030923A2/en active IP Right Grant
- 2003-09-12 AU AU2003299180A patent/AU2003299180A1/en not_active Abandoned
- 2003-09-12 EP EP03756489A patent/EP1558447B1/en not_active Expired - Lifetime
- 2003-09-12 JP JP2004540806A patent/JP2006501505A/en active Pending
- 2003-09-12 DE DE60315692T patent/DE60315692T2/en not_active Expired - Lifetime
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|---|---|---|---|---|
| US5380612A (en) * | 1992-05-18 | 1995-01-10 | Konica Corporation | Process for manufacturing planographic printing plate |
| WO1999021715A1 (en) * | 1997-10-29 | 1999-05-06 | Kodak Polychrome Graphics Company Ltd. | Manufacture of lithographic printing forms |
| US6007240A (en) * | 1998-04-14 | 1999-12-28 | Ta Instruments, Inc. | Method and apparatus for modulated-temperature thermomechanical analysis |
| US6251559B1 (en) * | 1999-08-03 | 2001-06-26 | Kodak Polychrome Graphics Llc | Heat treatment method for obtaining imagable coatings and imagable coatings |
| US20020098288A1 (en) * | 2000-06-30 | 2002-07-25 | Fuji Photo Film Co., Ltd. | Method of manufacturing lithographic printing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004030923A3 (en) | 2004-05-13 |
| JP2006501505A (en) | 2006-01-12 |
| EP1558447B1 (en) | 2007-08-15 |
| DE60315692T2 (en) | 2008-06-05 |
| WO2004030923A2 (en) | 2004-04-15 |
| EP1558447A2 (en) | 2005-08-03 |
| CN1688450A (en) | 2005-10-26 |
| AU2003299180A1 (en) | 2004-04-23 |
| DE60315692D1 (en) | 2007-09-27 |
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