CN101652251A - Method for making a lithographic printing plate precursor - Google Patents

Abstract

A method for making a lithographic printing plate precursor is disclosed comprising the steps of : - providing a grained and anodized aluminum support; - treating the support with an aqueous solutioncomprising a compound containing a silicate anion and one or more cations; - treating the support with an aqueous solution comprising a compound containing an organic acid group and/or an ester or a salt thereof; applying a coating on to said treated support comprising an image-recording layer including hydrophobic thermoplastic polymer particles having a particle size ranging between 20 nm and 55nm.

Description

Make the method for Lighographic printing plate precursor

Technical field

[0001] the present invention relates to make the method for temperature-sensitive and/or photosensitive printing version (printing plate) precursor.

Background technology

[0002] offset press uses so-called stencil paper (printing master), as is installed in the galley on the cylinders of printing press.Negative has lithographic image in its surface, obtains printed matter on the printable fabric by printing ink being applied to described image and printing ink being transferred to from negative, and printable fabric is generally paper.In routine so-called " wet method " lithographic printing, offer by oleophylic the printing ink and the damping aqueous solution (being also referred to as damping liquid) (or hydrophobic, promptly accept printing ink and repel water) lithographic image formed of zone and hydrophilic (or oleophobic, promptly accept water and repel printing ink) zone.In so-called anhydrous lithographic printing (driographic printing), lithographic image is made up of the zone of accepting printing ink and obstruct printing ink (ink-abhesive) (repulsion printing ink) and during anhydrous lithographic printing, only printing ink is offered negative.

[0003] stencil paper exposes the image forming material that (image-wise exposure) and processing is called printing plate precursor (plate precursor) by imaging usually and obtains.In later 1990s, except that known being suitable for is used for the photosensitive forme (so-called pre-sensitization forme) that UV contact exposes by film masks, it is very welcome that the temperature-sensitive plate precursor also becomes.Such thermo-sensitive material (thermal material) provides the advantage of sunlight stability and is used in particular for the direct seal carving version of so-called computer (computer-to-plate) method, wherein printing plate precursor is directly exposed, and does not promptly use film masks.Make material be exposed to heat or be exposed to infrared light and the heat of generation triggers (physics) chemical process, as ablating, polymerization, by not dissolving of crosslinked polymer, solubilising that heat causes or the particle by thermoplastic polymer latex condense (coagulation).

[0004] the most general temperature-sensitive forme by at the exposed region of coating and the poorly soluble abnormity that heat in alkaline developer causes between the exposed region become image.Coating comprises the lipophile base-material usually, and for example phenolic resins exposes by imaging, rate of dissolution or reduction (negative plate-making) or the raising (positive plate-making) of lipophile base-material in developer.During processing, dissolubility difference causes non-image (non-printing) regional removing of coating, thereby exposes hydrophilic support, and the image of coating (printing) zone is retained on the carrier.The representative instance of such forme for example is described among the EP-A 625728,823327,825927,864420,894622 and 901902.As for example described in the EP-A 625,728, the negative of such thermo-sensitive material plate-making embodiment often need expose and develop between preheating step.

[0005], do not need the negative plate-making printing plate precursor of preheating step can comprise the make a plate image recording layer of (work) of particles coalesce (coalescence) that the heat by thermoplastic polymer particles (latex) causes as for example described in the EP-A 770 494,770 495,770 496 and 770 497.These patent disclosures make the method for lithographic plate, said method comprising the steps of: (1) imaging exposes and to comprise the hydrophobic thermoplastic polymer particle that is dispersed in the hydrophilic base-material and can make light be converted into the image-forming component of the compound of heat, (2) and develop by applying the element that fountain solution and/or printing ink exposes imaging.

[0006] some in these by the use of thermal means can be carried out platemaking and for example based on one or more layers the ablation in the coating under not having the situation of wet-treating.At exposed region, bottom surface is exposed, and it has and is different from the affinity to printing ink or fountain solution that does not expose coating surface.

[0007] other by the use of thermal means that can carry out platemaking under not having the situation of wet-treating for example is based on the method that hydrophilic that one or more layers the heat in the coating causes transforms, and is not exposing the affinity to printing ink or fountain solution at coating surface place so that produce to be different from exposed region.

[0008] EP-A 1 614 538 has described negative lithographic printing plate precursor, carrier or its coating that has hydrophilic layer and provide thereon on possess hydrophilic property surface are provided for it, coating comprises image recording layer, described image recording layer comprises hydrophobic thermoplastic polymer particle and hydrophilic base-material, the particle mean size that it is characterized in that hydrophobic thermoplastic polymer particle is 45nm to 63nm, and the amount of the hydrophobic thermoplastic polymer particle in the image recording layer is 70wt% at least, with respect to image recording layer.

[0009] EP-A 1 614 539 and EP-A 1 614 540 have described the method for making lithographic plate, and it may further comprise the steps: (1) imaging exposes the image-forming component and (2) that are disclosed among the EP-A 1 614 538 develops the element of imaging exposure by applying alkaline aqueous solution.

[0010] WO2006/037716 has described the method for preparing negative lithographic printing version, it comprises the steps: that (1) imaging exposes the image-forming component and (2) that comprise the hydrophobic thermoplastic polymer particle that is dispersed in the hydrophilic base-material and light can be converted into hot compound and develops to the element that picture exposes by applying sol solution; The particle mean size that it is characterized in that thermoplastic polymer particles be 40nm to 63nm and wherein the amount of hydrophobic thermoplastic polymer particle greater than 70wt% and less than 85wt%, with respect to image recording layer.

[0011] undocumented European patent application EP-A 06 114 473 (applying date is 24-05-2006) discloses plate precursor, it comprises thermoplastic polymer particles and the infrared Absorption dyestuff of particle mean size less than 40nm, the latter under the situation of the counter ion of not considering to choose wantonly, quantity greater than 0.80mg/m ²The total surface of hydrophobic granule.

[0012] undocumented EP-A 06 122 415 (applying date 17-10-2006) discloses thermosensitive negative lithographic printing plate precursor, it is included in the image recording layer on the carrier, described image recording layer comprises hydrophobic thermoplastic polymer particle, infrared Absorption dyestuff and comprises the compound or its salt of aromatics part and at least one acidic-group, and has maximum to the red shift optical absorption peak under the wavelength of 300nm-450nm.Undocumented EP-A 06 122 423 (applying date 17-10-2006) discloses thermosensitive negative lithographic printing plate precursor, it is included in the image recording layer on the carrier, described image recording layer comprise hydrophobic thermoplastic polymer particle, infrared Absorption dyestuff and have the regulation structure and the maximum under 451nm-750nm to the dyestuff of red shift optical absorption peak.

[0013] EP 1 247 644 discloses a kind of lithographic plate, it comprises carrier, described carrier is subjected to Hydrophilic Surface Treatment by being immersed in the aqueous solution, the described aqueous solution comprises one or more hydrophilic compounds, it is selected from the compound with sulfonic acid group, polyvinyl phosphonic acids, sugar compounds or silicate compound.Perhaps, can use to comprise alkali silicate the solution of the mixture of potassium zirconium fluoride or phosphate and inorganic fluorine compounds.

[0014] EP 1 142 707 discloses a kind of method; control by special processing in the density of the micropore of the anodic oxide coating place of granulation and anodized alumina supporter existence by this method; as handle carrier (processing is widened in the hole) in acid or aqueous alkali, it can be to handle with hydrophilic compounds such as polyvinyl phosphonic acids, the compound that contains sulfonic acid group and sugar compounds subsequently.After processing is widened in the hole, can carry out the hole encapsulation process.

[0015] JP 2005/063518 discloses the method for making photosensitive planographic plate, and it may further comprise the steps, and handles granulation and anodized alumina supporter, dry support under 150-230 ℃ temperature subsequently with sodium metasilicate and polyvinyl phosphonic acids.

[0016] relevant with the negative Plate making printing version of the mechanism plate-making of latex-coalescent (coalescence) that causes according to heat main problem is its lower sensitivity (sensitivity).The sensitivity that discloses such galley in the prior art can improve by applying the coating that comprises the hydrophobic thermoplastic particle with small particle diameter.Yet comprise the reduction widely of shelf-lifeing that plate precursor obtained of so little hydrophobic thermoplastic particle.

Summary of the invention

[0017] target of the present invention provides the method that a kind of manufacturing has the heat-sensitive lithographic printing plate precursor of improved negative plate-making of shelf-lifeing.

[0018] this target realizes by claim 1, that is, a kind of method of making Lighographic printing plate precursor, it comprises the steps:

-granulation and anodized alumina supporter be provided;

-with comprising the aqueous solution processing carrier that comprises silicate anion and one or more cationic compounds;

-handle carrier with the aqueous solution that comprises the compound that contains organic acid groups and/or its ester or salt;

-applying to be coated with and expect described processed carrier, it comprises image recording layer, this image recording layer comprises that particle size is the hydrophobic thermoplastic polymer particle of 20nm-55nm.

[0019] according to the present invention; find the galley that comprises according to the carrier of prior art post processing than such surprisingly; improved shelf-lifeing of galley significantly; described galley comprises granulation and anodized alumina supporter; it is at first with comprising that the aqueous solution that comprises silicate anion and one or more cationic compounds handles, and handles with containing the compound that comprises organic acid group and/or the aqueous solution of its ester or salt subsequently.

[0020] from the following detailed description of embodiment preferred of the present invention, it is more obvious that further feature of the present invention, element, step, characteristic and advantage will become.

The specific embodiment

[0021] carrier of Lighographic printing plate precursor is granulation and anodized alumina supporter.Carrier can be that flaky material such as forme or its can be shaped element such as sleeve, and it can slide around printing cylinder of printing machine.Alumina supporter has the thickness of about 0.1-0.6mm usually.Yet this thickness can suitably change, and this depends on the size of employed galley and/or the size that plate precursor exposes forme logging machine (plate-setters) thereon.

[0022] aluminium preferably comes granulation by the electrochemistry granulation, comes anodization by the anodization technology of using sulfuric acid or sulfuric acid/phosphate mixture.The granulation of aluminium and anodization are very well-known in the art.

[0023] by making alumina supporter granulation (or roughening), the bonding force of printing image and the wetting characteristics of non-image areas all improve.Voltage by changing electrolytical type and/or concentration and applied in granulation step can obtain dissimilar particles.Surface roughness usually is expressed as arithmetic average centre line roughness degree Ra (ISO 4287/1 or DIN 4762) and can changes between 0.05 and 1.5 μ m.Aluminium base of the present invention preferably have be lower than 0.45 μ m, more preferably be lower than 0.40 μ m, also more preferably be lower than 0.30 μ m and most preferably be lower than the Ra value of 0.25 μ m.The preferably about 0.1 μ m of the lower limit of Ra value.More details about the preferred Ra value on the surface of granulation and anodized alumina supporter are described among the EP 1 356 926.

[0024] by the anodized aluminum carrier, its wearability and hydrophily have been improved.Al ₂O ₃The layer microstructure and thickness by the anodization step measurements, anode weight (g/m ², the Al that on the aluminium surface, forms ₂O ₃) 1 and 8g/m ²Between change.In the present invention, anode weight preferably 〉=3g/m ², more preferably 〉=3.2g/m ²Also more preferably 〉=3.5g/m ²Most preferably 〉=4.0g/m ²

[0025] best ratio between the particle mean size of the aperture on the surface of alumina supporter and (providing thereon) hydrophobic thermoplastic particle can improve the printing life-span of galley and can improve the toning performance of printed matter.The average pore size on the surface of alumina supporter is preferably 0.05: 1 to 1.0: 1 with this ratio of the particle mean size of (existing) thermoplastic granulates in the image recording layer of coating, more preferably 0.10: 1 to 0.80: 1 and most preferably 0.15: 1 to 0.65: 1.

[0026] according to the present invention, carrier is at first with comprising the aqueous solution processing that contains silicate anion and one or more cationic compounds (compd A).Silicate anion preferably wherein one or more center silicon atoms by electronegative part anion of centering on of fluorine or oxygen atom for example.Silicate anion preferably is selected from phosphosilicate (phosphosilicates), orthosilicate (orthosilicates), metasilicate (metasilicates), hydrogenated silicate (hydrosilicates), polysilicate (polysilicates) or mesosilicate (pyrosilicates).One or more cations make compound electroneutral and preferably be selected from alkali metal, Mg, Be, Zn, Fe, Ca, Al, Mn or Zr and/or its mixture.Especially, alkali metal such as sodium, potassium and lithium are preferred.Especially, preferred compound herein is alkali metal orthosilicate such as sodium orthosilicate or potassium and alkali metal silicate such as sodium metasilicate or potassium.

[0027] aqueous solution that contains compd A can comprise the hydroxide of suitable quantity such as NaOH, potassium and/or lithium so that increase the pH value.Described solution can further comprise alkali salt or the 4th family (IVB) slaine.Alkali salt is, for example, and water miscible salt such as nitrate (strontium nitrate, magnesium and barium), sulfate, hydrochloride, phosphate, acetate, oxalates and borate.The 4th family (IVB) slaine is, for example, titanium tetrachloride, titanium trichloride, titanium potassium fluoride (titanium potassium fluoride), titanium potassium oxalate (titanium potassium oxalate), titanium sulfate, titanium tetrachloride, basic zirconium chloride (zirconium chloroxide), zirconium dioxide, zirconium oxychloride (zirconium oxychloride) and zirconium chloride or the like.These alkali salts and the 4th family (IVB) slaine can use separately or with its two or more being used in combination.

[0028] aqueous solution concentration preferably that comprises compd A is 5-100g/l, and more preferably concentration is 10-50g/l and has the value at the pH of 25 ℃ of preferred 10-13.Handle preferably to be performed such, for example,, carrier impregnation is reached preferably 0.5-40 second in the described aqueous solution 20-100 ℃ preferred temperature and more preferably 25-50 ℃, and 1-20 second more preferably.

[0029] after handling carrier with the aqueous solution that comprises compd A, carrier is further with comprising that the compound that contains organic acid groups and/or the aqueous solution of its ester or salt (compd B) handles.Its suitable example comprises such compound, and it comprises hydroxy-acid group and/or phosphonyl group, or their salt.The suitable example that comprises the compound of hydroxy-acid group such as hydroxycarboxylic acid group is gluconic acid, citric acid or tartaric acid.Suitable example with compound of phosphonyl group is represented by following formula I or its salt:

And wherein:

R ¹And R ²Be hydrogen, optional substituted have straight chain, side chain, ring-type or Heterocyclylalkyl, halogen, hydroxyl, optional substituted aryl or the heteroaryl of 8 carbon atoms at the most independently;

R ³Be optional substituted have straight chain, side chain, ring-type or Heterocyclylalkyl, halogen, hydroxyl, optional substituted aryl or heteroaryl, carboxyl, phosphonyl group, phosphate group, sulfate group or the sulfonic acid group of 8 carbon atoms at the most.

[0030] on straight chain, side chain, ring-type or the Heterocyclylalkyl or the optional substituting group that on aryl or heteroaryl, exists be halogen such as chlorine or bromine atom, hydroxyl, amino, (two) alkyl amino, alkoxyl, carboxyl, sulfonic acid group, sulfate group, phosphate group and phosphonyl group.Aryl or heteroaryl may further include alkyl as optional substituting group.

[0031] in a more preferred embodiment, the compound with phosphonyl group is represented by formula II or its salt:

And wherein:

R ⁴And R ⁵Be hydrogen, optional substituted have straight chain, side chain, ring-type or Heterocyclylalkyl, halogen, hydroxyl, optional substituted aryl or the heteroaryl of 8 carbon atoms at the most independently.

[0032] on straight chain, side chain or ring-type or the Heterocyclylalkyl or the optional substituting group that on aryl or heteroaryl, exists be halogen such as chlorine or bromine atom, hydroxyl, amino, (two) alkyl amino, alkoxyl, carboxyl, sulfonic acid group, sulfate group, phosphate group and phosphonyl group.Aryl or heteroaryl may further include alkyl as optional substituting group.

[0033] in the most preferred embodiment, the compound with phosphonyl group is represented by formula III or its salt:

And wherein:

R ⁶Be hydrogen, optional substituted straight chain, side chain, ring-type or Heterocyclylalkyl or optional substituted aryl or heteroaryl independently.

[0034] on straight chain, side chain or ring-type or the Heterocyclylalkyl or the optional substituting group that on aryl or heteroaryl, exists be halogen such as chlorine or bromine atom, hydroxyl, amino, (two) alkyl amino, alkoxyl, carboxyl, sulfonic acid group, sulfate group, phosphate group and phosphonyl group.Aryl or heteroaryl may further include alkyl as optional substituting group.

[0035] the specific compound that is particularly suitable for being used for the present invention is following compound c om-1 and com-2.

[0036] preferably, compd B is polymer and/or its ester or the salt that comprises the constitutional repeating unit that contains organic acid group.Its suitable example comprises phosphonate ester, polyacrylic acid, polymethylacrylic acid and the acrylic acid of polyvinyl phosphonic acids, polyvinyl methylphosphonic acid, polyvinyl alcohol and the copolymer of vinyl phosphonate.It is highly preferred containing the polyvinyl phosphonic acids or gathering (methyl) acrylic acid solution.

[0037] use the processing of the aqueous solution comprise compd B preferably to be undertaken by following manner, impregnated carrier in the described aqueous solution for example, the concentration of the described aqueous solution is preferably 0.5-100g/l, and more preferably concentration is 1-50g/l; Preferably 20-120 ℃ of dipping temperature, more preferably 50-100 ℃; Dip time is 1-120s preferably, more preferably 2-60s.

[0038] in highly preferred embodiment, carrier is at first with the solution-treated that comprises alkali metal orthosilicate (orthosilicate) or alkali metal silicate (metasilicate), subsequently with comprising polyvinyl phosphonic acids or poly-(methyl) acrylic acid solution-treated.

[0039] especially, the solution that is used for the anode post processing also can comprise material such as chelating agent, tannic acid, sulfuric acid, fluoride and other additive, and these are known for the lithographic performance of improving substrate.

[0040] for applying anode post-treatment solution (post anodic solution), except that highly preferred dip-coating carrier, can use various other coating techniques, as spraying, seam be coated with, contrary roller coat cloth or electrochemistry coating.In these coating techniques, preferred spraying.Also be preferred by method once, because they help avoid pollution, otherwise described the pollution may occur owing to the recirculation of solution.

[0041] Lighographic printing plate precursor of the present invention is included in the thermal sensitivity coating on the hydrophilic support.Described thermal sensitivity coating comprises hydrophobic thermoplastic polymer particle, and the latter preferably is dispersed in the hydrophilic base-material.Coating can comprise one layer or more and comprise that the layer of hydrophobic thermoplastic polymer particle is called as image recording layer in this article.

[0042] because the heat that forms during exposing step, thermoplastic polymer particles can fusion (fuse) or is condensed (coagulate) so that form anti-developer phase, and it is corresponding to the printing zone of galley.Condense (coagulation) can come from coalescent (coalescence), the softening or fusing (melting) that the heat of thermoplastic polymer particles causes.Thermoplastic polymer particles preferably has the particle mean size that is lower than 200nm, is preferably 10nm to 75nm, more preferably 15nm to 65nm and most preferably 20nm to 55nm.Thermoplastic polymer particles preferably has the particle mean size less than 45nm, more preferably less than 38nm with most preferably less than 36nm.Granularity is defined as particle diameter, measures by photon correlation spectroscopy (being also referred to as accurate elasticity or dynamic light scattering).The amount that is present in the hydrophobic thermoplastic polymer particle in the image recording layer of coating is preferably 60wt% at least, more preferably is 70wt% at least and 80wt% at least most preferably.Perhaps, the amount of the hydrophobic thermoplastic polymer particle in the image recording layer of coating is 65wt%-85wt%, more preferably, and 75wt%-85wt%.With respect to the weight of the whole components in the image recording layer, measure the percentage by weight of thermoplastic polymer particles.

[0043] thermoplastic polymer particles hydrophobic polymer preferably, it is selected from polyethylene, polyvinyl chloride, poly-(methyl) methyl acrylate, poly-(methyl) ethyl acrylate, polyvinylidene chloride (poyvinylidene chloride), poly-(methyl) acrylonitrile, polyvinylcarbazole, polystyrene or its copolymer.According to a kind of preferred embodiment, thermoplastic polymer particles comprises the polystyrene or derivatives thereof, comprises the mixture or derivatives thereof of polystyrene and poly-(methyl) acrylonitrile, or comprises the copolymer or derivatives thereof of polystyrene and poly-(methyl) acrylonitrile.Can comprise the polystyrene of 50wt% at least at rear copolymer, more preferably the polystyrene of 65wt% at least.In order to obtain to the organic chemicals that uses in the forme cleaning agent such as enough tolerances of hydrocarbon, thermoplastic polymer particles preferably includes the nitrogenous unit of 5wt% at least, described in EP 1 219 416, the nitrogenous unit of 30wt% at least more preferably is as (methyl) acrylonitrile.According to the most preferred embodiment, thermoplastic polymer particles is made up of styrene and acrylonitrile unit basically, and its weight ratio is that (styrene: acrylonitrile), for example ratio was 2: 1 in 1: 1 to 5: 1.

[0044] weight average molecular weight of thermoplastic polymer particles can be 5,000 to 1,000,000g/mol.

[0045] is present in that thermoplastic polymer particles in the coating can be applied to that lithographic printing base plate (lithographic base) is gone up with the form of the dispersion in aquifer coating liquid and can be by being disclosed in US 3,476,937 or EP 1 217 010 in method prepare.The other method that is particularly useful for making the aqueous dispersion of thermoplastic polymer particles comprises:

-thermoplastic polymer is dissolved in organic water-immiscible solvent,

-the solution that will obtain like this be dispersed in the water or in the water-bearing media and

-remove organic solvent by evaporation.

[0046] coating also preferably includes hydrophilic base-material, and it preferably dissolves in the aqueous developer.The example of suitable hydrophilic base-material is following homopolymers and copolymer: vinyl alcohol, acrylamide, NMA, methylol methacrylamide, acrylic acid, methacrylic acid, hydroxy-ethyl acrylate, hydroxyethyl methacrylate and maleic anhydride/vinyl methyl ether copolymer.

[0047] coating preferably also comprises one or more compounds, and it absorbs infrared light and the energy that is absorbed is converted into heat.The amount of the infrared absorbing agents in the coating is 0.25-25.0wt% preferably, more preferably is 0.5-20.0wt%.Infrared absorbing compounds may reside in image recording layer and/or optional other layer.Preferred IR absorption compound is dyestuff such as cyanine (cyanine), merocyanine (merocyanine), indoaniline (indoaniline), oxonol, pyrans (pyrilium) and squaric acid (squarilium) dyestuff or pigment such as carbon black.The example of suitable infrared absorbing agents for example is described in the following document: EP 823 327, EP 978 376, EP 1,029 667, EP 1 053 868, EP 1 093 934; WO 97/39894 and WO 00/29214.Infrared absorbing dye, it becomes strong painted and form visual picture thus after exposing by infrared radiation or heating, also is to make the people interested and be described in widely among EP 1 614541 and the PCT2006/063327.Another preferred IR compound is following cyanine dye IR-1:

[0048] except that image recording layer, coating also can comprise one or more extra play.Except that the optional light absorbing zone that comprises the compound that one or more can be converted into infrared light heat, coating also can comprise protective layer such as cover layer, and it is removed during processing.This layer protective finish surface is avoided mechanical damage especially, and is generally included at least a water soluble binders, as polyvinyl acetate, gelatin, carbohydrate or the hydroxyethylcellulose of polyvinyl alcohol, polyvinylpyrrolidone, partial hydrolysis.Protective layer can produce in any known mode, as producing by the aqueous solution or dispersion, and can comprise a small amount of, promptly less than 5wt%, organic solvent.The thickness of protective layer advantageously is 5.0 μ m, preferably 0.1-3.0 μ m, particularly preferably 0.15-1.0 μ m at the most.Coating may further include for example bonding improving layer between image recording layer and carrier.

[0049] randomly, coating can further comprise other composition such as surfactant, perfluorinated surfactant especially, colouring agent, silica or titanium particle or polymer beads such as delustering agent and spacer.Especially, add colouring agent such as dyestuff or pigment, it provides visible color and is retained in after procedure of processing in the exposed region of coating to coating, is useful.Therefore, on galley, form visual picture and the inspection of (developed) galley of having developed in this step becomes possibility at the image-region that is not removed during the procedure of processing.The representative instance of such comparative dye is amino three or the triarylmethane colouring matters that replaces, for example crystal violet (crystal violet), gentian violet (methyl violet), Victoria's ethereal blue (victoria pure blue), fiexoblau 630, basonylblau 640, auramine (auramine) and peacock green (malachitegreen).In addition, the dyestuff of thoroughly discussing in the detailed description of EP 400 706 is suitable comparative dye.The dyestuff that combines with special additive, it is painted strongly that it only makes painted slightly but this coating of coating become after exposure, also is to make the people interested.

[0050] preferably, image recording layer includes organic compounds, it is characterized in that described organic compound comprises at least one phosphonyl group or at least one phosphate group or its salt, described in undocumented european patent application 05109781 (applying date is 2005-10-20).In particularly preferred embodiments, image recording layer comprises the organic compound represented as above formula III.These compounds may reside in the image recording layer, and its quantity is: 0.05-15wt%, and 0.5-10wt% preferably, 1-5wt% more preferably is with respect to the gross weight of the composition of image recording layer.

[0051] coating, more preferably image recording layer may further include light stabilizer or antioxidant.Light stabilizer or antioxidant preferably are selected from the space hindered phenol, hindered amine as light stabilizer (HALS) and their N-oxyl (oxyl) group, tocopherol, hydroxy amine derivatives, as hydroxamic acid and substituted azanol, hydrazides, thioether, the organic phosphorus compound of trivalent such as phosphite ester and reductone (reductones).In particularly preferred embodiments, light stabilizer is a reductone.Most preferably, light stabilizer is ascorbic acid or the arabo-ascorbic acid derivative according to formula IV:

Formula IV

R wherein ¹And R ²Be hydrogen atom, optional substituted alkyl, optional substituted alkenyl, optional substituted alkynyl, optional substituted aralkyl, optional substituted alkaryl, optional substituted heterocyclic radical or optional substituted heteroaryl independently.R ¹And R ²It can be the necessary atom that forms carbocyclic ring or heterocycle.

[0052] in the most preferred embodiment, R ¹And R ²It all is C-1 to C-5 alkyl.Described alkyl is meant the whole possible variant for the carbon atom of each number in the alkyl, that is, and and for 3 carbon atoms: n-pro-pyl and isopropyl; For 4 carbon atoms: n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methyl butyl; Or the like.

[0053] stabilizing agent according to formula IV preferably adds with following quantity: 1-100mg/m ², 2-50mg/m more preferably ², 5-25mg/m most preferably ²

[0054] representative instance according to the light stabilizer of formula IV is as follows:

[0055] can use any coating process two or more coating solutions to be applied to the water-wetted surface of carrier.(at once) is coated with several coatings solution simultaneously by each layer of coating/drying one after the other or by at once, can apply laminated coating.In drying steps, removing volatile solvent from coating is (the dry to the touch) of self-supporting (self-supporting) and feel drying up to coating.Yet, in drying steps, remove whole solvents optional (and even may not be possible).In fact, residual solvent content can be counted as other composition variable, by this variable, can optimize said composition.Drying is usually undertaken by hot-air is blown on the coating, usually at least 70 ℃, suitably 80-150 ℃ and especially under 90-140 ℃ the temperature.Can use infrared lamp in addition.Usually can be 15-600 second drying time.

[0056] between coating and drying, perhaps behind drying steps, heat treatment and cooling subsequently can provide other benefit, described in WO99/21715, EP-A 1074386, EP-A1074889, WO00/29214 and WO/04030923, WO/04030924, WO/04030925.

[0057] plate precursor of the present invention directly imaging be exposed to heat, for example,, perhaps undertaken by infrared light indirectly, by means of for example LEDs or infrared laser by means of heat head (thermal head).By the compound of aforesaid absorbing IR light, infrared light preferably is converted into heat.Preferably, use such laser instrument, its emission wavelength is the near infrared light of the about 1500nm of about 700-, for example, and semiconductor laser diode, Nd:YAG or Nd:YLF laser instrument.Most preferably, use emitted laser device between 780-830nm.Needed laser power depends on the sensitivity of image recording layer, the pixel action time of laser beam, (this was by spot diameter (representative value of the modern forme logging machine (plate-setters) under the maximum intensity of 1/e2: 10-25 μ m) measure), the resolution ratio of scan speed and exposing device (is the number of the addressable pixel of per unit air line distance, usually represents with dots per inch or dpi; Representative value: 1000-4000dpi).

Laser instrument-exposing device of [0058] two type is used usually: interior (ITD) and external drum (XTD) forme logging machine.The ITD forme logging machine (plate-setters) that is used for the temperature-sensitive forme usually is characterised in that very high sweep speed, up to 500 meter per seconds, and can need several watts laser power.Have the XTD forme logging machine (plate-setters) that the temperature-sensitive forme of the typical laser power of the about 1W of about 200mW-uses and under lower sweep speed, turn round, for example, the 0.1-10 meter per second.The XTD forme logging machine that is equipped with one or more laser diodes of launching in the 750-850nm wave-length coverage is the particularly preferred embodiment of the inventive method.

[0059] known forme logging machine can be used as off-line-printing machine (off-press) exposing device, and it provides the benefit of printing machine downtime of reducing.The configuration of XTD forme logging machine also can be used for online-printing machine and exposes, and this provides the benefit of the direct registration (immediate registration) in multicolour press.More ins and outs of online-printing machine exposing device for example are described in US 5,174,205 and US 5,163,368 in.

[0060] after exposure, by means of suitable treat liquid such as alkaline aqueous solution, precursor is developed, remove the non-image areas of coating whereby; Development step can combine with mechanical friction, for example by using rotating brush.During developing, also removed any water soluble protective layer that exists.

[0061] preferred aqueous base developers is the silicate-type developer, and the ratio of its silica and alkali metal oxide is at least 1 and pH 〉=11.Preferred alkali metal oxide comprises Na ₂O and K ₂O and its mixture.Particularly preferred silicate-type developer solution is the developer solution that comprises sodium metasilicate or potassium, that is, wherein the ratio of silica and alkali metal oxide is 1 silicate.Developer can randomly comprise other component, as buffer substance, complexing agent, defoamer, a spot of organic solvent, anticorrisive agent, dyestuff, surfactant and/or hydrotropic solubilizer (hydrotropic agents), as known in the art.Preferred surfactants comprises non-ionic surface active agent such as Genapol C 200 (trade mark of Clariant GmbH) and amphoteric surfactant such as librateric AA30 (trade mark of Libra Chemicals Limited).

[0062] in the automatically processing device of in as this area, using always, develops and preferably under 20-40 ℃ temperature, carry out.Use therein in the embodiment of silicate-type developer,, can suitably use the alkali metal silicate solutions of alkali metal content as 0.6-2.0mol/L in order to regenerate.These solution can have the silica/alkali metal oxide ratio identical with developer (yet, lower usually) and equally randomly comprise other additive.The regrown material of aequum must be suitable for employed developing apparatus, the forme day output, and image area etc., and be generally every square metre of printing plate precursor of 1-50mL/.For example, can regulate the interpolation of replenishers by the electrical conductivity of measuring developer, described in EP 0 556 690.

[0063] galley also may be used the fresh water or the aqueous solution, and for example, sol solution develops.Sol solution usually is liquid, aqueous, and it comprises one or more surface protection compounds, and it can protect the lithographic image of galley to avoid polluting or damaging.The suitable example of such compound is film-forming hydrophilic polymer or surfactant.Sol solution preferably has the pH value of 4-10, more preferably 5-8.Preferred sol solution is described among the EP 1342568.

[0064] or, plate precursor can directly be placed on the printing machine after the exposure and by printing ink and/or fountain solution are provided to precursor on printing machine (on-press) develop.

[0065] more details about development step for example are found in EP 1614538, EP1614539, EP 1614540 and WO/2004071767.

[0066] development step can be cleaning step and/or gluing step (gummingstep) subsequently.The gluing step comprises the post processing of the lithographic plate that uses aforesaid sol solution.

[0067] printing plate precursor can be with suitable correction agent as known in the art or anticorrisive agent post processing.Also extend thus its moving commentaries on classics cycle (run length) for the resistance that improves finished product galley, layer can be heated to high temperature (so-called " baking ").During baking procedure, can under the temperature of the glass transition temperature that is higher than thermoplastic granulates, heat forme, for example, reached 40 minutes-5 minutes at 100 ℃-230 ℃.Preferred baking temperature is higher than 60 ℃.For example, exposure and the forme that develops can toast 5 minutes under 230 ℃, toasted 10 minutes down or toasted 30 minutes down at 120 ℃ at 150 ℃.Baking can be carried out in the hot-air furnace of routine or be undertaken by the irradiation that is used in the lamp of launching in infrared or the ultraviolet spectra.Because this baking procedure, galley increases the resistance of the curable printing-ink of forme cleaning agent, correction agent and UV-.Hot post processing so for example is described among DE 1447963 and the GB 1 154 749.

[0068] galley that obtains like this can be used for conventional so-called wet offset printing (wetoffset printing), and wherein printing ink and moisture damping liquid are provided for forme.So-called single fluid printing ink is used in another suitable printing process, and does not have damping liquid.Suitable single fluid printing ink has been described in US 4,045,232; US 4,981,517 and US 6,140,392 in.In the most preferred embodiment, single fluid printing ink comprises the printing ink phase, is also referred to as hydrophobic or the oleophylic phase, with polyalcohol mutually, described in WO 00/32705.

Embodiment

Embodiment 1

1. prepare reference substrate AS-01.

Make the thick aluminium foil degreasing of 0.3mm by the following method: cleaned 3.6 seconds with the aqueous solution spraying 6 seconds that contains 34g/l NaOH and with demineralized water at 70 ℃.In 8 seconds, make this paper tinsel electrochemistry granulation then, use alternating current, containing 15g/l HCl, 15g/l SO ₄ ^2-Ion and 5g/l Al ³⁺In the aqueous solution of ion, at 37 ℃ temperature and about 100A/dm ²(about 800C/dm ²Charge density) under.Then, make the aluminium foil desmut by the following method: cleaned 4 seconds with the aqueous solution etching 5 seconds of the sulfuric acid that contains 145g/l and with demineralized water at 80 ℃.This paper tinsel was containing in the aqueous solution of sulfuric acid of 145g/l temperature and the 33A/dm at 57 ℃ subsequently in 10 seconds ²Current density (330C/dm ²Charge density) under carry out anodic oxidation, then with demineralized water washing 7 seconds with 120 ℃ of dryings 7 seconds.Obtained reference substrate AS-01.

2. preparation back anode is handled (PAT) substrate AS-02 to AS-07.

Subsequently, undressed substrate AS-01 is immersed in Na-silicate (silicate) solution (seeing below), and dipping temperature is 30 ℃, and dip time is 10 seconds, produces substrate AS-02 to AS-04 (table 1).By the substrate of further handling with PVPA solution-treated silicate (seeing below), it is 5 seconds (table 1) with dip time that dipping temperature is 70 ℃, has obtained substrate AS-05 to AS-07.

After each impregnation steps, back anode is handled sample and is carried out drying with demineralized water cleaning 5 seconds and according to the condition described in the table 1.

The surface roughness Ra of the carrier of Huo Deing is that 0.35-0.4 μ m (using interferometer NT1100 to measure) and anode weight are 4.0g/m like this ²

The Na-silicate solutions:

Working concentration is sodium orthosilicate ((Natriumsilikat 5/2, the commercially available Roland N.V that derives from) solution in demineralized water of 25g/l.This solution is called as " Na-silicate solutions " in this article.

PVPA solution:

Working concentration is the solution of PVPS 100 (polyvinylphosphonic acid, the trade mark of Clariant GmbH) in demineralized water of 20g/l.This solution is called as " PVPA solution " in this article.

Table 1: substrate AS-02 to AS-07

The Al substrate	??PAT ??Sol.1	Baking temperature ℃	Second drying time	??PAT ??Sol.2	Baking temperature ℃	Second drying time
							??AS-02	Na-silicate	Room temperature	To doing	??-	??-	??-
??AS-03	Na-silicate	??120	??180	??-	??-	??-
							??AS-04	Na-silicate	??160	??180	??-	??-	??-
??AS-05	Na-silicate	Not dry	Not dry	??PVPA	Room temperature	To doing
							??AS-06	Na-silicate	Not dry	Not dry	??PVPA	??120	??180
??AS-07	Na-silicic acid	Not dry	Not dry	??PVPA	??160	??180

The Al substrate	??PAT ??Sol.1	Baking temperature ℃	Second drying time	??PAT ??Sol.2	Baking temperature ℃	Second drying time
								Salt

3. prepare latex LX-01.

Polymer emulsion is by the semi-continuous emulsion polymerizing preparation, and wherein all monomer (styrene and acrylonitrile) is added in the reactor.Before beginning to add monomer, all surfaces activating agent (3%, with respect to amount of monomer) is present in the reactor.In 2 liters double jacket reactor, (SDS Ultra Pure, by Alkemi BV, Lokeren is Belgium) with 1243.9 demineralized waters that restrain to add 10.8 NaLSs that restrain.Reactor uses nitrogen wash and heating up to 80 ℃.When reactor content reaches 80 ℃ temperature, add 5% sodium persulfate aqueous solution of 12 grams.Subsequently, 80 ℃ of reactor heatings 15 minutes.Then, in 180 minutes, according to dosage add monomer mixture (acrylonitrile of the styrene of 238.5 grams and 121.5 grams).Simultaneously, during monomer adds, add the persulfate aqueous solution (5% Na of 24 grams in addition ₂S ₂O ₈The aqueous solution).Monomer add finish after, 80 ℃ of reactor heatings 30 minutes.Be the quantity of minimizing residual monomer, add redox-initiator system (being dissolved in 1.55 sodium formaldehyde sulphoxylate dihydrates (SFS) that restrain of 120 gram water and the 70wt% tert-butyl hydroperoxides (TBHP) that restrain with 22.5 grams water-reducible 2.57).In 80 minutes, add the aqueous solution of SFS and TBHP respectively.Added thermal response then 10 minutes and be cooled to room temperature subsequently again.The Proxyl ultra (5-bromo-5-nitro-1,3-dioxane (dioaxane)) that adds 100ppm filters latex as antimicrobial and use coarse filter paper.

This has obtained latex dispersion, its solid content be 20.84% and the pH value be 3.46.Particle mean size be 36nm (use Brookhaven BI-90 analyzer to measure, the commercially available Brookhaven Instrument Company that derives from, Holtsville, NY, USA.).

4. prepare plate precursor PPP-02 to PPP-07.

Be prepared as follows the coating solution that is used for plate precursor PPP-02 to PPP-07: added latex dispersion LX-01 to demineralized water and dispersion that stirring obtained 10 minutes.Subsequently, add the IR-dyestuff and, add polyacrylic acid solution stirring this solution after 60 minutes.After stirring 10 minutes, add DEQUEST 2010 solution and subsequently after stirring 10 minutes again, add surfactant solution.Stir coat dispersions again 30 minutes and regulated pH value to 3.6.Table 2 has been listed the dry coating weight of the heterogeneity of coating.

The coating solution that is obtained uses painting cloth-knife to be coated on the Al-substrate AS-02 to AS-07 with wet thickness 30 μ m subsequently.After 60 ℃ of dryings, this has obtained plate precursor PPP-02 to PPP-07.

Table 2: dry coating weight.

Composition	??g/m 2
		Latex LX-01 (1)	??0.540
IR-dyestuff IR-2 (2)	??0.108
		Polyacrylic acid (3)	??0.081
??DEQUEST?2010(4)	??0.025
		Surfactant (5)	??0.005
		Amount to (g/m 2)	??0.759

(1) latex LX-01, as in above the 3rd synthesize;

(2) IR aqueous dye solutions, it comprises the IR-2 of 1wt%:

(3) aqueous solution, it comprises polyacrylic acid (PAA) (Aquatreat AR7H, the commercially available National Starch﹠amp that derives from of 5wt%; Chemical Company);

(4) aqueous solution, it comprises the ethoxy di 2 ethylhexyl phosphonic acid (hydroxyethyl-diphosphonate) (HEDP, the commercially available Monsanto Solutia Europe that derives from) of 10wt%;

(5) aqueous surfactant solution, it comprises the fluorine surfactant ZonylFS0100 (trade mark of Dupont) of 5wt%.

5. expose and printing plate precursor PPP-02 to PPP-07.

In each plate precursor PPP-02 to PPP-07,80% relative humidity and 35 ℃ of following storages 7 days, these are " wearing out " plate precursor before exposure for a forme quilt exposure (" fresh " plate precursor) immediately and another forme.

All " fresh " and " wearing out " plate precursor is exposed to the fast kinetic head IR-of Creo TrendSetter 324440W laser forme logging machine, uses to expose serial 210-180-150-120-90mJ/cm ²@150rpm uses the addressability (addressability) of 2400dpi and 200lpi to shield (screen).The galley of these exposures is set directly on the Heidelberg GTO46 printing machine (can available from Heidelberger Druckmaschinen AG), and without any processing or preliminary treatment.Use compressibility backing plate (blanket) and use 3%Agfa Prima FS101 (trade mark of Agfa)+10% isopropyl alcohol (as fountain solution) and K+E 800 black ink (K﹠amp; The trade mark of E) prints.

Use following start-up course: at first use the dampening roller 5 of engagement to change, use the dampening roller of engagement and ink roller 5 to change then, begin printing then.On the 80g offset paper, carry out 1000 printings.

6. print result.

6.1 sensitivity.

Forme sensitivity is defined as minimum energy density, and under this minimum energy density, 2% is visible fully by means of the 5X magnifying glass in printing 1.000.Forme sensitivity all aging and that fresh forme is obtained is≤150mJ/m ²

6.2 the result of shelf-lifeing.

Measure shelf-lifeing of galley according to removing (clean-out) result who on aging galley, obtains.If the removing performance of forme is kept or only slightly descended after digestion period, then it has good shelf-lifeing.

For whole formes, the removing result that fresh contrast and galley PP-02 to PP-07 of the present invention are obtained is 5.The removing result measured to aged samples provides in table 3.

Table 3: the removing result of aging galley.

Galley	The Al substrate	Remove *
			PP-02 (Comparative Examples)	??AS-02	??0
PP-03 (Comparative Examples)	??AS-03	??0
			PP-04 (Comparative Examples)	??AS-04	??0
PP-05 (embodiment of the invention)	??AS-05	??4/5
			PP-06 (embodiment of the invention)	??AS-06	??4
PP-07 (embodiment of the invention)	??AS-07	??4

^*Removing is to use following standard to measure on printed sheet:

The complete black image of 0=under printing≤25 and printing 250;

1=color image but complete black image under printing 250 on printing serious under≤25;

The image of the serious colouring of 2=under printing≤25 and printing 250;

The image of the medium colouring of 3=under printing≤25 and printing 250;

4=is in 250 times slight colourings of printing;

The complete clean background of 5=under printing≤25 and printing 250.

And wherein be lower than 4 value and be not suitable for high-quality printing.

Result in the table 3 shows and uses single stage anode post processing (only Na-silicate is handled), can not obtain the suitable removing of forme after storage under the condition of warm moist, and this shows the difference of forme shelf-life (contrast galley PP-02 to PP-04).When at first carrying out post processing of Na-silicate anode and PVPA anode post processing subsequently, the removing performance after storage under the warm moist condition only drops to 4/5 slightly, and this shows good shelf-lifeing (galley PP-05 to PP-07 of the present invention).

Embodiment 2

1. preparation back anode is handled (PAT) substrate AS-08 to AS-16.

Undressed substrate AS-01 (referring to embodiment 1) is immersed in Na-metasilicate solution (seeing below), PVPA solution, PAA solution (seeing below) and/or the mixed solution (seeing below), according to the condition described in the table 4.The temperature of each in these solution is 70 ℃.

After impregnation steps separately, the substrate AS-08 to AS-16 that handles with demineralized water flushing back anode reaches 5 seconds and is at room temperature dry.

The composition of PVPA solution is described in embodiment 1.

Na-metasilicate solution:

Sodium metasilicate pentahydrate (the commercially available Van Baerle﹠amp that derives from; Co.ChemischeFabrik) be dissolved in the demineralized water, concentration is 25g/l.This solution is called as " Na-metasilicate solution " in this article.

PAA solution:

Working concentration is the solution of Aqualic AS58 (polyacrylic acid, the trade mark of Nippon Shokubai (Japan)) in demineralized water of 20g/l.This solution is called as " PPA solution " in this article.

Mix Na-metasilicate/PAA solution:

Use the solution of sodium metasilicate and polyacrylic mixture respectively with the concentration of 25g/l and 20g/l.

Mix Na-metasilicate/PVPA solution:

Use the solution of the mixture of sodium metasilicate and polyvinyl phosphonic acids respectively with the concentration of 25g/l and 20g/l.

Table 4: aluminium base AS-08 to AS-16.

The Al substrate	PAT solution 1	Dip time/second	PAT solution 2	Dip time/second
					The AS-08 Comparative Examples	??PAA	??5	??-	??-
The AS-09 Comparative Examples	??PVPA	??5	??-	??-
					The AS-10 Comparative Examples	The Na-metasilicate	??10	??-	??-
The AS-11 Comparative Examples	Na-metasilicate+PAA	??10	??-	??-
					The AS-12 Comparative Examples	Na-metasilicate+PVPA	??10	??-	??-
The AS-13 Comparative Examples	??PAA	??5	The Na-metasilicate	??10
					The AS-14 Comparative Examples	??PVPA	??5	The Na-metasilicate	??10
AS-15 the present invention	The Na-metasilicate	??10	??PAA	??5
					AS-16 the present invention	The Na-metasilicate	??10	??PVPA	??5

2. prepare latex LX-02.

In 8 liters double jacket reactor, add 40.0g lauryl sodium sulfate (SDSUltra Pure, available from Alkemi BV, Lokeren, Belgium) and the demineralized water of 5495.3g.Reactor is with nitrogen wash and be heated to 75 ℃.When reactor content reaches 75 ℃ temperature, add the styrene of 15.9 grams and the mixture (i.e. 1.5% total monomer amount) of 8.1 acrylonitrile that restrain and prepare the latex kind.After mixing 10 minutes, for the monomer that makes interpolation evenly disperses, add part initiator solution (initator of 50% total quantity), that is, and 5% sodium persulfate aqueous solution of 105.6 grams.During 30 minutes, reactor is heated to 80 ℃ subsequently, subsequently during 180 minutes in, dosage adds the monomer mixture of the acrylonitrile of the styrene of 1044.1 grams and 531.9 grams.Simultaneously, also in 180 minutes, dosage adds 5% sodium peroxydisulfate solution of 105.6 grams.After finishing monomer and adding, 80 ℃ of reactor heatings 30 minutes.Be to reduce the quantity of residual monomer, add redox-initiating system: the usefulness water-reducible t-butyl hydroperoxide of 100g (TBHP) solution that is dissolved in the 70wt% of the sodium sulfoxylate formaldehyde dihydrates (SFS) of 6.99 grams of 534g water and 11.43g.In 80 minutes, add the aqueous solution of SFS and TBHP respectively.Added thermal response then 10 minutes and be cooled to room temperature subsequently again.Interpolation is as the 5-bromo-5-nitro-1 of the 100ppm of antimicrobial, and 3-dioxane and use coarse filter paper filter latex.This has produced latex dispersion LX-02, and its solid content is that 20.74wt% and pH value are 2.99.Particle mean size is 41nm (using Brookhaven BI-90 analyzer to measure the commercially available Brookhaven Instrument Company that derives from, Holtsville, NY (USA)).

3. prepare plate precursor PPP-08 to PPP-16.

Be prepared as follows the coating solution of plate precursor PPP-08 to PPP-016: added latex dispersion LX-02 to demineralized water and dispersion that stirring obtained 10 minutes.Subsequently, add the IR-dyestuff, and after 60 minutes, add polyacrylic acid solution at agitating solution.After stirring 10 minutes, add DEQUEST 2010 solution and after 10 minutes, add surfactant solution in another stirring subsequently.Stir coat dispersions again 30 minutes and regulated pH value to 3.6.Table 5 is listed the dry coating weight of different coating composition.

The coating solution that is obtained is applied to Al substrate AS-08 to AS-16 subsequently, uses painting cloth-knife, with wet thickness 30 μ m.After 60 ℃ of dryings, this has produced plate precursor PPP-08 to PPP-16.

Table 5: dry coating weight.

Composition	??g/m 2
		Latex LX-02 (1)	??0.406
IR-dyestuff IR-3 (2)	??0.075
		Polyacrylic acid (3)	??0.056
??DEQUEST?2010(4)	??0.016
		??Ascorox(5)	??0.013
Surfactant (6)	??0.005
Total amount (g/m 2)	??0.571

(1) the latex LX-02 that synthesizes in the 2nd more than;

(2) IR aqueous dye solutions contains the IR-3 of 1wt%:

(3) contain the aqueous solution of the polyacrylic acid (PAA, Aqualic AS58, the trade mark of Nippon Shokubai (Japan)) of 5wt%;

(4) aqueous solution contains the 1-hydroxy ethylidene-1 of 10wt%, 1-diphosphonic acid (HEDP, the commercially available Monsanto Solutia Europe that derives from);

(5) antioxidant ST-01 (referring to above specification);

(6) aqueous surfactant solution, it comprises the fluorine surfactant ZonylFSO100 (trade mark of Dupont) of 5wt%.

4. expose and printing plate precursor PPP-08 to PPP-16.

In each plate precursor PPP-08 to PPP-16, forme exposed immediately (" fresh " plate precursor) and another forme before exposure in 80% relative humidity and 35 ℃ storage 7 days down; These are " wearing out " plate precursor.

All " fresh " and " wearing out " plate precursor is exposed to the fast kinetic head IR-of Creo TrendSetter 324440W laser forme logging machine, uses to expose serial 210-180-150-120-90mJ/cm ²@150rpm uses the addressability (addressability) of 2400dpi and 200lpi to shield (screen).The plate precursor of these exposures is set directly at (it is equipped with Kompac III dampening system (trade mark of VARN)) on the Heidelberg GTO46 printing machine, and does not carry out any processing or preliminary treatment.Use compressibility backing plate (blanket) and use 4%Emerald Premium 3520 (trade mark of Anchor) (as fountain solutions) and K+E800 black ink (K﹠amp; The trade mark of E) prints.

Use following start-up course: at first use the dampening roller 5 of engagement to change, use the dampening roller of engagement and ink roller 5 to change then, begin printing then.On the 80g offset paper, carry out 1000 printings.

5. print result.

5.1 sensitivity.

Forme sensitivity is defined as minimum energy density, and under this minimum energy density, 2% is visible fully by means of the 5X magnifying glass in printing 1.000.The forme sensitivity that whole fresh galley obtained is≤120mJ/m ²For contrast galley PP-10, PP-13 and PP-14, be difficult to measure sensitivity, because the removing performance of difference.

5.2 the result of shelf-lifeing.

Measure shelf-lifeing of galley according to the removing result who on aging galley, obtains.If the removing performance of forme is kept or only slightly descended after digestion period, then it has good shelf-lifeing.

The removing result that fresh contrast and galley PP-08 to PP-16 of the present invention are provided for whole formes, equals 5, and exception is contrast galley PP-10, PP-13 and PP-14, and it has bad removing performance.The removing result that aging contrast and galley of the present invention are obtained provides in table 6.

Table 6: the removing result of aging galley.

Galley	In typographic removing *
		PP-08 (Comparative Examples)	??3
PP-09 (Comparative Examples)	??2
		PP-10 (Comparative Examples)	??1
PP-11 (Comparative Examples)	??3
		PP-12 (Comparative Examples)	??2
PP-13 (Comparative Examples)	??0
		PP-14 (Comparative Examples)	??0
PP-15 (embodiment of the invention)	??4
		PP-16 (embodiment of the invention)	??4

^*Use following removing standard:

The complete black image of 0=under printing≤25 and printing 250;

1=color image but complete black image under printing 250 on printing serious under≤25;

The image of the serious colouring of 2=under printing≤25 and printing 250;

The image of the medium colouring of 3=under printing≤25 and printing 250;

4=is in 250 times slight colourings of printing;

The complete clean background of 5=under printing 250.

And wherein be lower than 4 value and be not suitable for high-quality printing.

Result in the table 6 shows:

-after storage under the warm moist condition, contrast galley PP-08 to PP-12 has provided the removing result of difference, these galleys comprise carrier, it has single stage anode post processing (Na-metasilicate solution, PVPA solution mixes Na-metasilicate/PAA solution or mixes Na-metasilicate/PVPA solution).

-after storage under the warm moist condition, contrast galley PP-13 to PP-14 has provided unacceptable removing result, and these galleys comprise carrier, and it at first also uses the metasilicate solution-treated subsequently with PVPA solution or PAA solution-treated.

-after storage under the warm moist condition, galley PP-15 to PP-16 of the present invention has provided good removing performance, and these galleys comprise carrier, and it at first also uses PVPA solution or PAA solution-treated subsequently with Na-metasilicate solution-treated.

Claims (10)

1. method of making Lighographic printing plate precursor, it comprises the steps:

(i) provide granulation and anodized alumina supporter;

(ii) with comprising that the aqueous solution that comprises silicate anion and one or more cationic compounds handles described carrier;

(iii) handle carrier with the aqueous solution that comprises the compound that contains organic acid groups and/or its ester or salt;

(iv) apply to be coated with and expect described processed carrier, it comprises image recording layer, and this image recording layer comprises that average particle size particle size is the hydrophobic thermoplastic polymer particle of 20nm-55nm.

2. according to the process of claim 1 wherein that the amount with respect to the hydrophobic thermoplastic polymer particle of composition gross weight that is present in the image layer is at least 70%.

3. according to each method in the aforementioned claim, wherein silicate anion is selected from phosphosilicate, orthosilicate, metasilicate, hydrogenated silicate, polysilicate or mesosilicate.

4. according to the method for claim 3, wherein silicate anion is orthosilicate or metasilicate.

5. according to each method in the aforementioned claim, wherein organic acid group is selected from hydroxy-acid group and/or phosphonyl group.

6. according to each method among the claim 1-5, wherein step compound (iii) is the polymer that comprises constitutional repeating unit, and it contains organic acid groups.

7. according to the method for claim 6, wherein polymer is polyvinyl phosphonic acids or poly-(methyl) acrylic acid.

8. according to each method in the aforementioned claim, wherein carrier have the Ra value that is lower than 0.45 μ m and 〉=3.2g/m ²Anode weight.

9. method of making lithographic plate, it comprises the steps:

(i) provide plate precursor according to the method for claim 1-8;

(ii) described plate precursor is exposed to light and/or heat;

(iii) randomly use treat liquid that the precursor of described exposure is developed.

10. printing process, it comprises the steps:

(i) provide galley according to the method for claim 9;

(ii) be arranged on the galley that is obtained on the printing machine and provide printing ink and/or fountain solution.