CN100439119C - Method of making a lithographic printing plate precursor - Google Patents
Method of making a lithographic printing plate precursor Download PDFInfo
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- CN100439119C CN100439119C CNB038237067A CN03823706A CN100439119C CN 100439119 C CN100439119 C CN 100439119C CN B038237067 A CNB038237067 A CN B038237067A CN 03823706 A CN03823706 A CN 03823706A CN 100439119 C CN100439119 C CN 100439119C
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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
-
- 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
- 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
- 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
- B41C2201/12—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by non-macromolecular organic compounds
-
- 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
- B41C2210/04—Negative working, i.e. the non-exposed (non-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
- B41C2210/24—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 involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/12—Preparation of material for subsequent imaging, e.g. corona treatment, simultaneous coating, pre-treatments
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Printing Plates And Materials Therefor (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention discloses a method of producing a heat-sensitive lithographic board precursor, which includes the following steps: (1) The net of a lithographic carrier, which has a hydrophilic surface, is provided; (2) Coating containing phenolic resin is coated on the hydrophilic surface of the net; (3) The coating is dried by supplying heat onto the coated net; (4) In the cooling step, the temperature of the net is reduced at a speed higher than the average cooling speed of the net stored under the environmental condition but not higher than 30 DEG C / s; (5) The precursor is wound on a reel or cut into slices. The cooling step notably increases the aging property of the precursor. Short after coating, stable sensitivity can be achieved.
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 fed 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 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 film masks, 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, and especially for the direct plate-making method of so-called computer, wherein plate front body is directly exposed, and does not promptly use film masks.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, regional coating that the difference of solubility has caused removing non-image (non-printing), thus expose 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-A625728,823327,825927,864420,894622 and 901902.
The step of industrial production plate precursor comprises launches a volume mesh carrier material (it is aluminium typically), coat one or more layers coating 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 the 559 controlled slow coolings that disclose after heat treatment provide extra improvement.According to the one piece of file in back, " controlled slow cooling " is meant that velocity ratio that heat is lost from the precursor upper reaches cool off and wants slowly under environmental condition.The example of this type of cooling means is included in isolates material after the heat treatment or is placed in the baking oven slowly to be cooled to lower temperature.Such cooling procedure will continue several hrs, and can only " off-line " carry out, and is about to the volume of thin slice or is deposited 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 cooling step that provides, this step 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 realizes by the method for following technical proposals 1, it is characterized in that dry coating is through online cooling step.According to the present invention, disclosed in the prior art and long cooling step that can only off-line carry out is substituted by online cooling step, wherein Wang temperature descends with the average cooling rate that is higher than the net of preserving under the environmental condition, but is not higher than 30 ℃/s.
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 obviously the embodiment that combines with extra off-line cooling step of online cooling step according to the present invention is within the scope of the present invention.
Specific embodiments of the present invention defines in following technical proposals.
Technical scheme:
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) by apply heat to have a coating come dry coating on the net;
(iv) cooling step initiatively, wherein Wang temperature reduces with the average cooling rate that is higher than the net of preserving under environmental condition, still is not higher than 30 ℃/s;
(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 average cooling rate is not higher than 20 ℃/s.
3, according to the method for technical scheme 1, wherein average cooling rate is not higher than 10 ℃/s.
4, according to each method of technical scheme 1-3, wherein the temperature of net is higher than Tg when cooling step begins, Tg is the glass transition temperature that contains the coating of phenolic resins, and during cooling step, the temperature of net drops to T2 from T1, T1 is higher than Tg and T2 is lower than Tg, and average cooling rate is lower than 10 ℃/s.
5,, wherein during cooling step, reduce the temperature of net according to the method for technical scheme 4:
-drop to T1 in the phase I with the average cooling rate of at least 10 ℃/s; With
-drop to T2 with the average cooling rate that is lower than 10 ℃/s from T1 in second stage.
6,, wherein during cooling step, reduce the temperature of net according to the method for technical scheme 4:
-drop to T1 in the phase I with the average cooling rate of at least 10 ℃/s; With
-drop to T2 with the average cooling rate that is lower than 10 ℃/s from T1 in second stage; And
-drop to about environment temperature with the average cooling rate of at least 10 ℃/s from T2 in the phase III.
7, according to the method for technical scheme 4, wherein the cooling from T1 to T2 is carried out with the average cooling rate that is lower than 5 ℃/s.
8, according to the method for technical scheme 4, wherein T1 is Tg+20 ℃, and T2 is Tg-20 ℃.
9, according to the method for technical scheme 4, wherein T1 is Tg+10 ℃, and T2 is Tg-10 ℃.
10, according to the method for technical scheme 4, also comprise step (iii) and the heating steps of step between (iv), wherein during described heating steps, remain on more than the glass transition temperature of phenolic resins in the temperature of 0.1-60 Intranet second.
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 the layer that one or more layers the following examples are discussed.Phenolic resins can be present in one or more layers of described coating.
The mentioned any precursor temperature of this paper is regarded the mentioned carrier and the temperature of coating 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, big radiator as coating, whether and the temperature of coating equals or is in close proximity to the temperature of carrier, no matter by heat or cold coated side or the back side or the two sides heating or the cooling step that carry out this paper discussion to precursor are provided.In fact, the temperature value of this paper report writes down by thermocouple assembly being placed on the net back side, when installing all parts of process coating apparatus, and the remote-controlled temperature value of reading of this device.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 according to priority 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 drying steps finishes, preferably with the of short duration online additional heating steps of precursor process.Perhaps, precursor is cooled off between drying and heating steps earlier, but this is optional.During optional heating steps, to heat supply on the dry coating, so that the temperature of coating remains on the numerical value (temperature of surrounding air is defined as 20 ℃ at this paper) that is higher than the precursor of preserving under the environmental condition.So temperature the when temperature of precursor can be lower than the drying steps end during heating steps.More preferably, the temperature of coating remains on the numerical value of coating temperature when being higher than drying steps and finishing during heating steps.Perhaps, come dry coating is heat-treated by the length that prolongs drying machine so that extra dry air in coating exsiccation after-blow on coating.Temperature when in this embodiment, the coating temperature during the heat treatment can finish with drying steps equates.
During the online heating steps, preferably the net temperature with precursor is elevated to more than the glass transition temperature Tg of phenolic resins." Tg " is meant the glass transition temperature of the phenolic resins in the component at this paper, and coated, the dry and heating of component promptly contains the glass transition temperature of the coating of phenolic resins.Described Tg value can be measured fast by known calorimetry.Heat treatment should be enough of short duration so that can online implementation, for example in 0.1-60 second, more preferably in 1-30 second.Preferably, the temperature of netting during heating steps is elevated at least 150 ℃, 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.Hot-air and/or steam preferably have and are higher than 150 ℃ temperature, more 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.Cooling step is a cooling step quick, " initiatively ", promptly reduces the temperature of coating with the cooling velocity than the preceding height of preserving under the environmental condition.Therefore the cooling step of indication is defined as the step of initiatively cooling off between beginning and finishing herein.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 Tg.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.So the cooling step in the inventive method can be the sequence of one or more actives and passive cooling stage.In such multistage cooling procedure, with the active cooling step be defined as first initiatively cooling stage begin and the process of last active cooling stage between finishing.
The average cooling rate during cooling step or the cooling stage be defined as cooling step or cooling stage begin and finish between temperature difference and described cooling step or the ratio of cooling stage duration.
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 at the precursor up-draught.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.Also can use and form chilling roll, for example the low-heat material of heat conductivity perhaps by other material.But the back side of chilling roll contact net or coat side, or 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.
Now determined to be limited in by the inventor and be no more than 30 ℃/s, preferably be no more than 20 ℃/s and be most preferably not exceeding the ageing properties that 10 ℃/s can obtain to improve by value with average cooling rate.Therefore,, this reason is quickly cooled to it below Tg, then the content height of amorphous state if may relating to phenolic resins.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, just can explain the sensitivity offset that during material aging, can be observed towards lower.
On the other hand, consider high-speed, preferably of short duration, the fast cooling step of net through modern coating apparatus, this is because alternate manner can prolong the coating path greatly during cooling step length.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), cool off fast once more in seconds to reach about environment temperature at last.
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 the ageing properties that improves, the resistance that coating of materials according to the invention also demonstrates mechanical damage significantly improves.More particularly, improved rub resistance greatly by above-mentioned cooling procedure, in the cooling procedure near Tg is slow process at interval.
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.The cooling that air nozzle 10-11-12 can be used for adding: 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 according to exposure basically 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 image-region was etched, 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 development latitude 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 the list of references quoted of US 6,063,544 and these files.
According to another embodiment, plate precursor 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 developing, remove the exposure area and determined hydrophily non-image (non-printing) zone, and unexposed area is not removed and has been determined lipophile image (printing) zone from carrier from carrier.
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 anodised alumina supporter.Aluminium rough surface and anodic oxidation are known in the art.Anodised alumina supporter can improve its surperficial hydrophilic nmature through handling.For example, alumina supporter can (for example 95 ℃) be handled its surface by the silicic acid salinization with sodium silicate solution by at high temperature.Perhaps, phosphoric acid salt is handled, and it comprises with phosphate solution handles alumina surface, and phosphate solution can further contain inorganic fluoride.In addition, alumina surface can clean with citric acid or citrate 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 alumina surface 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-537 633, DE-A-4 001 466, EP-A-292 801, EP-A-291 760 and the US-P-4 458 005 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 that obtain 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 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 under every kind of situation 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 development accelerator and development restrainer.These compositions addings can be contained the layer of phenolic resins and/or other layer of coating.
Development 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 development capability 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, to 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-methyl benzenesulfonic acid, DBSA, to toluenesulfinic acid, ethyl sulfuric acid, phenyl-phosphonic acid, phenyl phosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, M-phthalic acid, adipic acid, paratolunitrile, 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, positive 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 the opposing agent of developing, and is also referred to as development restrainer, promptly can postpone one or more compositions of unexposed area dissolving in processing.The dissolving inhibitory action 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.The opposing agent of this type of can being developed adds the layer that contains phenolic resins or adds other layer of 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 the polymer that repels water, for example contains the polymer of siloxanes and/or perfluoroalkyl unit.In typical embodiment, precursor contains the barrier layer, and this layer comprises the polymer that repels water, 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 the polymer that repels water also repels ink, for example be polysiloxanes, then amount is 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 inhibition development capability 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, the polymer that repels water 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, TegoProtect 5001 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 the same composition as same solution with phenolic resins is used, also tends to the interface place that will self be positioned between coating and air, thereby forms independently top layer on coating.Simultaneously, this type of surfactant can improve the quality of coating as dispersant.Perhaps, can will be coated in second solution that contains phenolic resins layer top in the polymer applications of repelling water.In this embodiment, 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 phase of the repulsion 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 the dyestuff of for example cyanine and part cyanines or the pigment of carbon black for example.The example of suitable IR absorbent is described in for example EP-A-823327,978376,1029667,1053868,1093934; Among the WO 97/39894 and 00/29214.Preferred compound is following cyanine dye:
For the surface of protective finish, especially, can also randomly apply protective layer from mechanically infringement.Protective layer contains at least a water-soluble copolymer adhesive 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, promptly 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 service cycle 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 preferred painting method according to plan, coating layer thickness, coating composition and drying condition are formulated.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, 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.For specific purposes, can also use the mixture of above-mentioned solvent, 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 probe 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 influence the dissolution velocity of coating in developer basically by the irradiation visible light.Most preferably, coating is insensitive to the daylight of environment, and promptly visible light (400-750nm) and nearly UV line (300-400nm) are in intensity and irradiation time corresponding to normal running conditions, so can handle 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 (benzoquinones) two trinitride or diazonium (diazo) 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 coating in the exposure area.
Plate precursor of the present invention can be shone infrared ray by the mode of for example LED or laser instrument.Most preferably, the light that is used to expose is the wavelength that emitted by laser instrument at the approximately near infrared ray of 750-1500nm, for example semiconductor laser diode, Nd:YAG or Nd:YLF laser instrument.Required laser power depends on the sensitivity of image recording layer, the pixel duty time of laser beam, and it can (in maximum intensity be 1/e by spot diameter
2Condition under, the exemplary value that modern plate is 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) determine.
The general laser irradiating device that uses two types: interior drum (ITD) and external drum (XTD) plate control point adjustment.The characteristic feature that the ITD plate that is used for hot plate is provided with device is the laser power up to several watts of the very high sweep speed of 500m/sec and needs.The XTD plate control point adjustment that is used for hot plate is in low sweep speed, and for example the 0.1-10m/sec operation has the typical laser power of about 200mW to about 1W down.
Known plate control point adjustment can be used as (off-press) exposure sources of disembarking, and its advantage has been to reduce the downtime of printing machine.XTD plate governor arrangements also is used in machine (on-press) exposure, and its advantage is rapid registering 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 developing, can also remove any water soluble protective layer of 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, corrosion inhibiter, dyestuff, surfactant and/or hydrotropic solvent.Preferred temperature is being developed according to the convention of prior art in the processing unit under 20-40 ℃ automatically.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 developing apparatus, 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 of the present invention can be carried out post processing with suitable correction agent commonly known in the art or anticorrisive agent subsequently.The resistance of the galley of finishing for raising, thus the print run cycle 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-curing (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, described in WO 00/32705, the single liquid ink contains the ink phase, is also referred to as hydrophobic or the oleophylic phase, with polyalcohol mutually.
Embodiment
Following composition is coated in routine through surface roughening and anodised alumina supporter on the net, and 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(comparative 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, then through optional heating and cooling step.During heating steps, the air that will have temperature shown in the table 1 in 1.2 seconds blows on the coating.In embodiment 1 and 2, 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 average cooling rate process Tg.
Then material is gone up in different-energy density at Creo Trendsetter 3244 (830nm) imaging down is set.Exposed plate speed with 0.84m/min on Agfa Autolith PN85 processor uses Agfa Ozasol EP26 developer to handle down at 25 ℃, uses Agfa Ozasol RC795 gluing at last.Regulation IR-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 showing board in the wavelength maximum of dyestuff in the exposure area.The sensitivity of the material of in fate as shown in table 1, measuring freshly prepd material and under environmental condition, wearing out.
Table 1
The material that data in the table 1 show according to the present invention cooling 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
Also can prove the ageing properties of its raising through the heat treatment of off-line by after using method of the present invention, making material.Obtain embodiment 4,5 and 6 by applying identical composition and carrying out drying according to the described same steps as of front embodiment.Then, use additional drier (135 ℃ hot-air is blown on the dry coating) that the material of drying is heat-treated.Between the heat treatment and chilling roll cooling of back, net is cooled off under environmental condition, so that the temperature of net will be 118 ℃ before the cylinder cooling.The metal roller acquisition phase I that remains on numerical value shown in the table 2 with temperature cools off fast.Material contacts 2.41s with chilling roll.Through passing through the slow cooling of second stage behind the metal chilling roll immediately, this stage is by during the 32s 50 ℃ air being blown on the coating.
Table 2
In 7 days, measuring sensitivity on the freshly prepd material and on the material that artificial off-line is aging under the temperature that provides in table 3.Data in the table 3 show that slowly the material (promptly using the higher chilling roll of temperature) of cooling has more stable ageing properties.Embodiment 6 is cooled off in the interval near Tg with cooling velocity very slowly, obtained best ageing properties, this is because extra off-line heat treatment is worked hardly.
Table 3
| Embodiment | 0 |
7 days, 20 |
7 days, 25 |
7 days, 30 ℃ |
| 4 | 17 | 159 | 210 | 222 |
| 5 | 87 | 167 | 200 | 226 |
| 6 | 101 | 210 | 220 | 233 |
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) by apply heat to have a coating come dry coating on the net;
(iv) cooling step initiatively, wherein Wang temperature reduces with the average cooling rate that is higher than the net of preserving under environmental condition, still is not higher than 30 ℃/s;
(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 average cooling rate is not higher than 20 ℃/s.
3, according to the process of claim 1 wherein that average cooling rate is not higher than 10 ℃/s.
4, according to each method of claim 1-3, wherein the temperature of net is higher than Tg when cooling step begins, Tg is the glass transition temperature that contains the coating of phenolic resins, and during cooling step, the temperature of net drops to T2 from T1, T1 is higher than Tg and T2 is lower than Tg, and average cooling rate is lower than 10 ℃/s.
5,, wherein during cooling step, reduce the temperature of net according to the method for claim 4:
-drop to T1 in the phase I with the average cooling rate of at least 10 ℃/s; With
-drop to T2 with the average cooling rate that is lower than 10 ℃/s from T1 in second stage.
6,, wherein during cooling step, reduce the temperature of net according to the method for claim 4:
-drop to T1 in the phase I with the average cooling rate of at least 10 ℃/s; With
-drop to T2 with the average cooling rate that is lower than 10 ℃/s from T1 in second stage; And
-drop to about environment temperature with the average cooling rate of at least 10 ℃/s from T2 in the phase III.
7, according to the method for claim 4, wherein the cooling from T1 to T2 is carried out with the average cooling rate that is lower than 5 ℃/s.
8, according to the method for claim 4, wherein T1 is Tg+20 ℃, and T2 is Tg-20 ℃.
9, according to the method for claim 4, wherein T1 is Tg+10 ℃, and T2 is Tg-10 ℃.
10, according to the method for claim 4, also comprise step (iii) and the heating steps of step between (iv), wherein during described heating steps, remain on more than the glass transition temperature of phenolic resins in the temperature of 0.1-60 Intranet second.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02102414.6 | 2002-10-04 | ||
| EP02102414 | 2002-10-04 | ||
| US60/420,135 | 2002-10-22 |
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| CN1688449A CN1688449A (en) | 2005-10-26 |
| CN100439119C true CN100439119C (en) | 2008-12-03 |
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| CNB038237067A Expired - Fee Related CN100439119C (en) | 2002-10-04 | 2003-09-12 | Method of making a lithographic printing plate precursor |
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| EP (1) | EP1551643B1 (en) |
| JP (1) | JP4338640B2 (en) |
| CN (1) | CN100439119C (en) |
| AU (1) | AU2003299181A1 (en) |
| DE (1) | DE60318600T2 (en) |
| WO (1) | WO2004030924A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| EP2065211B1 (en) | 2007-11-30 | 2010-05-26 | Agfa Graphics N.V. | A method for treating a lithographic printing plate |
| ES2430562T3 (en) | 2008-03-04 | 2013-11-21 | Agfa Graphics N.V. | Method for manufacturing a support of a lithographic printing plate |
| ATE514561T1 (en) | 2008-03-31 | 2011-07-15 | Agfa Graphics Nv | METHOD FOR TREATING A LITHOGRAPHIC PRINTING PLATE |
| ATE553920T1 (en) | 2009-06-18 | 2012-05-15 | Agfa Graphics Nv | LITHOGRAPHY PRINTING PLATE PRECURSOR |
| JP2011073211A (en) * | 2009-09-29 | 2011-04-14 | Fujifilm Corp | Method of manufacturing original planographic printing plate |
| EP2329951B1 (en) | 2009-12-04 | 2012-06-20 | AGFA Graphics NV | A lithographic printing plate precursor |
| CN103328214B (en) | 2011-01-25 | 2015-06-17 | 爱克发印艺公司 | A lithographic printing plate precursor |
| EP2489512B1 (en) | 2011-02-18 | 2013-08-28 | Agfa Graphics N.V. | A lithographic printing plate precursor |
| WO2014106554A1 (en) | 2013-01-01 | 2014-07-10 | Agfa Graphics Nv | (ethylene, vinyl acetal) copolymers and their use in lithographic printing plate precursors |
| 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 |
| EP2963496B1 (en) | 2014-06-30 | 2017-04-05 | Agfa Graphics NV | A lithographic printing plate precursor including ( ethylene, vinyl acetal ) copolymers |
| ES2655798T3 (en) | 2014-12-08 | 2018-02-21 | Agfa Nv | System to reduce ablation waste |
| EP3130465B1 (en) | 2015-08-12 | 2020-05-13 | Agfa Nv | Heat-sensitive lithographic printing plate precursor |
| EP3157310A1 (en) | 2015-10-12 | 2017-04-19 | Agfa Graphics Nv | An entry sheet for perforating electric boards such as printed circuit boards |
| EP3170662B1 (en) | 2015-11-20 | 2019-08-14 | Agfa Nv | A lithographic printing plate precursor |
| EP3430474A1 (en) | 2016-03-16 | 2019-01-23 | Agfa Nv | Method and apparatus for processing a lithographic printing plate |
| EP3637188A1 (en) | 2018-10-08 | 2020-04-15 | Agfa Nv | An effervescent developer precursor for processing a lithographic printing plate precursor |
| EP3778253A1 (en) | 2019-08-13 | 2021-02-17 | Agfa Nv | Method for processing a lithographic printing plate |
| EP4239411A1 (en) | 2022-03-04 | 2023-09-06 | Eco3 Bv | Method and apparatus for processing a lithographic printing plate precursor |
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|---|---|---|---|---|
| WO1999021715A1 (en) * | 1997-10-29 | 1999-05-06 | Kodak Polychrome Graphics Company Ltd. | Manufacture of lithographic printing forms |
| EP1074889A2 (en) * | 1999-08-03 | 2001-02-07 | Kodak Polychrome Graphics Company Ltd. | Thermal treatment of imagable coatings |
| 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 |
-
2003
- 2003-09-12 CN CNB038237067A patent/CN100439119C/en not_active Expired - Fee Related
- 2003-09-12 WO PCT/EP2003/050622 patent/WO2004030924A1/en active IP Right Grant
- 2003-09-12 EP EP03798935A patent/EP1551643B1/en not_active Expired - Fee Related
- 2003-09-12 AU AU2003299181A patent/AU2003299181A1/en not_active Abandoned
- 2003-09-12 JP JP2004540807A patent/JP4338640B2/en not_active Expired - Fee Related
- 2003-09-12 DE DE60318600T patent/DE60318600T2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999021715A1 (en) * | 1997-10-29 | 1999-05-06 | Kodak Polychrome Graphics Company Ltd. | Manufacture of lithographic printing forms |
| EP1074889A2 (en) * | 1999-08-03 | 2001-02-07 | Kodak Polychrome Graphics Company Ltd. | Thermal treatment of imagable coatings |
| 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 |
|---|---|
| DE60318600T2 (en) | 2009-01-15 |
| AU2003299181A1 (en) | 2004-04-23 |
| WO2004030924A1 (en) | 2004-04-15 |
| CN1688449A (en) | 2005-10-26 |
| JP2006501506A (en) | 2006-01-12 |
| JP4338640B2 (en) | 2009-10-07 |
| EP1551643B1 (en) | 2008-01-09 |
| DE60318600D1 (en) | 2008-02-21 |
| EP1551643A1 (en) | 2005-07-13 |
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