CN1314254A - Lithographic printing plate - Google Patents

Abstract

A lithographic printing plate forerunner is provided with an aluminium substrate by the processing roughening and anodization; a photographic layer provided on the surface of said substrate which contains an infra-red absorbent and a polymer solved in alkaline aqueous solution but not dissolved in water and the solubility in the alkaline developing solution is changed due to the exposal of the infra-red laser, wherein said substrate is obtained by electrochemistry roughening the aluminium alloy plate made of aluminium alloy with relative high purity of some trace element.

Description

Lithographic plate

The present invention relates to a kind of lithographic plate presoma, more specifically say, the present invention relates to a kind of lithographic plate that is used to produce the laser version.

Recently, along with the development of imaging technique, people begin to be concerned about on the lithographic plate surface and directly form alphabetical manuscript, image or the like, use narrow limit laser beam flying lithographic plate simultaneously, do not use film and directly form lithographic plate.

As this image forming material, so-called pattern of fever eurymeric lithographic plate is arranged, wherein be present in the photographic layer infrared absorbing agents when when exposure by showing that its photo-thermal transformation produces heat, and being exposed the thermosol that part produced and forming erect image of photographic layer, also has pattern of fever minus lithographic plate, wherein free-radical generating agent and acid agent are owing to heat produces free radical and acid, and Raolical polymerizable and sour cross-linking reaction take place, cause that photographic layer is exposed the insoluble of part, forms negative-appearing image.In this pattern of fever imaging, laser radiation causes that the photo-thermal transformation substance in the photographic layer produces the heat that causes the imaging reaction.

The manufacturing of lithographic plate presoma (directly type lithographic plate presoma) that can make laser lithography is normally by changing into the aluminium flake rough surface corrugated form, the surface being carried out anodization, applied the formation photographic layer of photosensitive layer coating solution and drying thereon then.Then, the lithographic plate presoma of corrugated form is cut into the thin slice of required size, and a plurality of such sheet stackings are compressed then.Perhaps, to be rolled into after drum forms deposits, lithographic plate is cut into required size.The lithographic plate presoma that will compress and ship by laser explosure carries out the image printing processing and the processing processing of developing, and is arranged on the printer then.

Yet roughening and the aluminium substrate that forms anodic film on it have the low problem of light sensitivity, and reason is as follows.Because the heat conductance of substrate is more much higher than photographic layer, so before substrate was used to form image fully, near the heat that is produced photographic layer and the substrate surface of contact just was diffused in the substrate.As a result, between photographic layer and the substrate decomposition reaction of the positive photographic layer at surface of contact place abundant inadequately, and film is stayed non-image part.

In addition, although also having a problem is that this pattern of fever recording layer must contain the infrared absorbing agents with photo-thermal conversion capability, but this absorbing agent is because molecular weight is relatively large and poorly soluble, and attached in the micropore in the anodization substrate and be difficult to therefrom remove.Therefore, film keeps easily in the development processing of using alkaline development solution.

For addressing this problem, carried out various fundamental researchs, so that in the situation of positive photographic layer, improve the developing performance of the photographic layer at surface of contact place between substrate and photographic layer.Yet, in any situation, all do not reach abundant gratifying degree.

Because the substrate of roughening is inhomogeneous, the tight exposure level between photographic layer and the substrate also descends.When closely cooperating between photographic layer and the substrate descended, after lithographic plate was produced, the ability of lithographic plate tolerance duplicate printing was lowered.Specifically,, compare, be difficult to guarantee contact with the tight of substrate with the photographic layer that needs lithographic plate to produce the lithographic plate of film aborning for directly writing the photographic layer of lithographic plate.Thus, need to improve the ability of tolerance duplicate printing.

In addition, studied the photosensitive material that can work recently under the safety light of azarin color, these photosensitive materials are compared by shorter wavelength with the conventional products that activates by the 500nm wavelength and are activated.Yet, by 450nm or short-wavelength activated and in JP patented claim 11-209822 in that describe and the photosensitive printed board that developed recently recently more, anodic film 450nm or more the light absorption under the short exposure wavelength be lower than absorbance log under about 500nm wavelength.Therefore, write in the picture carrying out the laser printing version, lithographic plate is subjected to the influence of light scattering easily, and forms on every side the thin image-region at so-called edge at each medium tone point.So, medium tone occurred and put the problem of whole chap, and the area of medium tone point is than increasing.

In the case, the light absorption that further increases anodic film is wise move, and must improve the volume of anodic film itself by aperture of reducing the so-called micropore that exists in the anodic film or the hole number of passing through to reduce per unit area for this reason.Yet, on the other hand, because the micropore of aluminium anode film attracts photographic layer to cause tight contact by the effect of anchor formula, the minimizing of the reduction of micropore size or per unit area micropore quantity can make with tight contact of photographic layer and loosen thus, so that structure can not be used in practice.Therefore, for obtaining to contact with the tight of substrate, it is necessary having a certain amount of micropore.So far, for forming image and, except that quality that reduces medium tone point and repeatability, not having other way used as galley.

In addition, when assembling the above-mentioned type of directly writing lithographic plate presoma, several lithographic plate presomas sections accurately must be stacked in the size of same regulation.For this reason, must several lithographic plate presoma sections accurately be delivered in the size of same regulation.For carrying, often use conveying belt.Yet, the problem that exists the lithographic plate presoma to slide, and to carry accurately and pile up be difficult.In addition, although will use that conveying belt and conveying roller are used for that laser image is write, developed by the user, printing etc., and be used for the lithographic plate presoma is transferred to various processes, but the problem that exists is that the lithographic plate presoma may slide, thereby accurately to carry and pile up with these conveying belt and conveying roller be difficult, particularly in laser explosure, the degree of accuracy that needs high location, therefore the conveying of this difference not only causes throughput rate to descend but also causes formed image quality decrease.And in developing process, what use in most of situation is automatic transport type development machine, and this carries poor problem during also strong request being solved developing process.

An object of the present invention is to provide a kind of type lithographic plate presoma of directly writing, it can solve above-mentioned variety of issue.

The present inventor furthers investigate, and finds that above-mentioned purpose can realize by the aluminium substrate that use has a particular characteristic, and has obtained the present invention thus.

Lithographic plate of the present invention comprises: through roughened and anodized aluminium substrate and the photographic layer that is provided on the substrate surface, said photographic layer contains infrared absorbing agents and water insoluble and be dissolved in the polymkeric substance of alkaline aqueous solution, and its solubleness in alkaline development solution changes because of infrared laser exposure; Wherein substrate obtains by the aluminium alloy version electrochemical rougheningization that will contain 0.05-0.5wt%Fe, 0.03-0.15wt%Si, 60-300ppm Cu, 100-400ppm Ti and 10-200ppm Mg, contain at least a element in the column element under being selected from of 1-100ppm: Li, Na, K, Rb, Cs, Ca, Sr, Ba, Sc, Y, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Co, Rh, Ir, Pd, Pt, Ag, Au, C, Ge, P, As, S, Se, Te and Po, and aluminium purity is 99.0wt% or higher.

Through various researchs, the present inventor finds can reach at least a by in the above-mentioned element that adds trace to highly purified aluminium alloy uniform roughening when the alkali electrochemical roughened, and obtain the present invention thus.

In aspect said, for achieving the above object, lithographic plate of the present invention comprises above-mentioned substrate and above-mentioned photographic layer, and substrate has following characteristics (a) and at least one characteristic (b):

(a) substrate is 0.5 μ m or lower in the average roughness Ra of midline, and surface area is 2-30 per surface area doubly, (b) has micropore in the above-mentioned on-chip anodic film, and its aperture is 1-5nm, and hole density is 8 * 10 ¹⁵-2 * 10/m ²

By after anodization, carrying out method or other method that the micropore sealing is handled, obtain the aluminium substrate that surface area is a 2-30 times of per surface area (a) easily.According to the present invention, by reducing the surface roughness Ra of roughening substrate, make the thickness of photosensitive coated layer even, prevented that the part in thick photographic layer zone (be not easy occur produce because of the laser absorption effect heat) from forming in these zones, and can effectively strengthen light sensitivity.

As a rule, concerning being used to print and (wherein said surface is used as the anodic film roughening of substrate through the surface of roughening, and said substrate is used for lithographic plate), its true surface area of measuring is the long-pending 40-100 of apparent surface times, yet, in the present invention, fall 2-30 times scope and reduced surface area thus, controlled the degree of depth and the size of the micropore in the anodization rete by making the relation between it.Can prevent the absorption of macromolecule infrared absorbing agents and invade the micropore further portion and be not easy to be developed the formation of the photographic layer of solution removal.The generation of residual film is inhibited, and the micropore in the anodization rete plays independently thermal insulation layer effect separately.So, reduced the heat conduction at photographic layer and substrate surface of contact place, and the heat that is produced is used for imaging reaction effectively, cause sensitization to strengthen thus.

As a rule, also use a kind of method in some cases, wherein handle the surface area that reduces the galley substrate by the micropore sealing, said micropore sealing is handled and is to use pressure (hydraulic) water steam treated or hot water treatment to reduce remaining color.Yet it is inaccessible that effect of the present invention is only handled by the micropore sealing.In the present invention, handle or another kind of disposal route by using the micropore sealing, the surface area of control substrate is fallen in the long-pending 2-30 of the apparent surface scope doubly it to reach outstanding effect of the present invention.In addition, it is found that by control surface roughness (Ra) falls in the preferable range less than 0.5 μ m it, can prevent the local decline of the light sensitivity that causes owing to photographic layer is in uneven thickness, and can make the whole zone of photographic layer obtain uniform ISO.

In addition, the one side of lithographic plate presoma for achieving the above object of the present invention is a kind of lithographic plate presoma that comprises substrate and above-mentioned photographic layer, wherein vertical average surface roughness Ra of substrate reverse side is with laterally average surface roughness Ra is different, suppose and to be expressed as Ral than the average surface roughness Ra on the big average surface roughness direction, average surface roughness Ra on the less average surface roughness direction is expressed as Ras, and then Ral and Ras satisfy the following relationship formula:

1.1≤Ral/Ras≤5.0

In lithographic plate presoma of the present invention, vertical average surface roughness Ra of substrate reverse side is with laterally average surface roughness Ra is different mutually, and Ral and Ras satisfy the above-mentioned relation formula.When lithographic plate presoma of the present invention was carried by conveying belt or conveying roller, the vertical and horizontal effect on the substrate reverse side had different friction force.Because the friction force effect at substrate reverse side upper edge vertical and horizontal is different mutually, the slip in can effectively preventing to carry and sinuous.(here, " wriggle " and be meant when presoma is transferred and direction that it should be transferred is certain angle.)

In addition, one side for achieving the above object of the present invention is a kind of lithographic plate presoma that comprises substrate and photographic layer, said photographic layer has laser-photosensitive and is set on the substrate, wherein the reverse side to substrate carries out slight surface treatment, handled zone is at least from the side of substrate reverse side one side, and width is more than or equal to 1mm and smaller or equal to 50mm.

In lithographic plate presoma of the present invention, the reverse side of substrate has at least one zone through the preset width of slight roughening at the side of a side.When carrying lithographic plate presoma of the present invention by conveying belt or conveying roller, effect has different friction force between slight roughened area on the substrate reverse side and non-roughened area.Because the friction force effect at substrate reverse side side place is big, during carrying, can effectively prevent sliding stop and sinuous.

In the lithographic plate presoma aspect above-mentioned two, when photographic layer is can when using the scratch photographic layer of 30g load, preferably form 0.1g/m on the substrate reverse side by using cut tester (sapphire pin 0.5mm φ) in test ²Or more anodic film.

When the lithographic plate presoma with above-mentioned two aspects piled up and deposits, if reverse side and photographic layer come in contact, then photographic layer can not abraded by the part, and this is because of the scrambling that has equably on the whole surface of reverse side to a certain degree.Yet, if the part of a presoma reverse side is scratched, when presoma being piled up and deposit, just the local easily scratch of photographic layer.Same situation also occur in when presoma rolled-up and when depositing with drum forms.Therefore, by on reverse side, forming 0.1g/m ²Or more anodic film, can increase the skin hardness of reverse side, thereby reverse side is not easy to be scratched.When presoma being piled up and depositing or when rolling and depositing, can prevent the scratch of photographic layer with the form of cylinder.

Figure 1A and 1B are the skeleton views of another embodiment of lithographic plate presoma of the present invention.

Fig. 2 A and 2B are the sketches of lithographic plate presoma reverse side of the present invention.

Fig. 3 is an example of anodizing apparatus used in the lithographic plate presoma production method of the present invention.

Fig. 4 is the process flow diagram of an example of lithographic plate presoma production method of the present invention.

Fig. 5 is the basic structure sketch of cut tester.

Fig. 6 is the structural representation of an example of mechanically roughened device used when making the substrate be used for lithographic plate presoma of the present invention.

Fig. 7 is the synoptic diagram of the electrolysis unit in the two step automatic feed electrolytic process, and this method can be used for making the used substrate of lithographic plate presoma of the present invention.

To elaborate the present invention below. Aluminium substrate

Used aluminium substrate is the substrate that contains metal among the present invention, and said metal is that aluminum or aluminum alloy forms by the aluminium of dimensionally stable basically. Except the fine aluminium version, this substrate can also be selected from basically by aluminium and contain alloy version that the trace extraneous element forms and with plastic foil or the paper of aluminium (alloy) lamination or vapor deposition. In addition, it can also be by aluminum slice being attached to the compound foil of making on the polyethylene terephthalate film, described in JP patent (JP-B) 48-18327.

In the following description, will or have one deck by the substrate of aluminum or aluminum alloy manufacturing and be commonly referred to as aluminium substrate by the substrate of aluminum or aluminum alloy manufacturing layer.

Here, consist of the aluminium substrate of this substrate by aluminium alloy version electrochemical roughening is obtained, this aluminium alloy version contains 0.05-0.5wt%Fe, 0.03-0.15wt%Si, 60-300ppm Cu, 100-400ppm Ti and 10-200ppmMg, and contain at least a element in the column element: Li under being selected from of 1-100ppm, Na, K, Rb, Cs, Ca, Sr, Ba, Sc, Y, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Co, Rh, Ir, Pd, Pt, Ag, Au, C, Ge, P, As, S, Se, Te and Po, and aluminium purity is 99.0wt% or higher.

The purity of aluminium is 99.0wt% or higher, preferred 99.3wt% or higher, more preferably 99.5wt% or higher. Preferably be limited to above-mentioned element as the material that comprises in the aluminium alloy of lithographic plate presoma substrate, inevitably except the impurity, its content as above defines. As the inevitable impurity in the aluminium alloy, can be Ga, V, Ni etc. Preferably use the content of inevitable impurity to be 0.1wt% or littler aluminium alloy.

The substrate that is used for lithographic plate presoma of the present invention preferably contains 0.10-0.40wt% Fe, 0.05-0.10wt%Si, 100-200ppmCu, 150-300ppmTi and 40-180ppmMg, so that the close contact of acquisition and photosensitive layer.

The substrate that is used for lithographic plate presoma of the present invention preferably contains at least a element that is selected from above-mentioned element set of 1-100ppm. When the content of above-mentioned element during less than 1ppm, obtain the effect deficiency of the coarse form of even electrolysis, and the content that surpasses 100ppm is not preferred from the economic point of view. The content of above-mentioned element is preferably 5-100ppm, more preferably 10-100ppm.

When being selected from two or more element in the above-mentioned element set and adding in the aluminium alloy, control the separately content of element, so that its total content in substrate is 1-100ppm.

Preferred substrate can carry out molded operation by the molten bath to the aluminium alloy that contains above-mentioned elemental range and produces among the present invention. For improving the purity of aluminium alloy, the molten bath of preferred purified aluminium alloy. Purification process is for example, to be intended to remove the circulation (flux) of unnecessary gas such as hydrogen etc. in the molten bath and to process; Use the degassed processing of Ar gas, Cl gas etc.; Be intended to remove the filtration treatment of insoluble substance, use filter that so-called rigid media filter such as earthenware filter, ceramic foam filter etc., alumina wafer, alumina balls etc. make as filter material, glass filter etc.; And other. In addition, can unite and carry out the purification process that formed by above-mentioned degassed processing and filtration treatment.

Can add the element that is selected from above-mentioned element set (below, sometimes be called " trace element ") to above-mentioned molten bath, so that its content in aluminium alloy is positioned at above-mentioned scope. If carry out purification process, then preferably before purification step, add trace element.

The molded operation of aluminium alloy is undertaken by casting method usually. Casting method is enumerated the method (its representative method is the DC casting method) of using fixing casting and is used the method (its representative method is continuous casting process) that drives casting. In the method for using fixing casting, for example, obtain ingot bar in the molten bath impouring fixed mould with above-mentioned aluminium alloy, can form required form to processing such as ingot bar are rolled then. In using the method that drives casting, for example, can cast and rolling processing to the molten bath of aluminium alloy continuously by using two rollers and biobelt, it is molded as required form.

An example that shows below the DC casting molding methods of aluminium alloy.

At first, in the molten bath impouring fixed mould with aluminium alloy, will generate the ingot bar that thickness is 300-800mm. According to commonsense method the ingot bar of gained is cut into the dark superficial layer of 1-30mm, preferred 1-100mm. Then, can carry out immersion treatment if need. When carrying out immersion treatment, preferably set heating condition so that intermetallic compound can not become swollen, and preferably 450-620 ℃ of lower heat treated 1 hour or more grow to 48 hours or shorter. When being less than 1 hour, the effect of immersion treatment may be not enough.

If after the aluminium alloy ingot bar is through the immersion treatment that needs, can carry out hot rolling and cold rolling, to obtain the rolling plate of aluminium alloy. The initial temperature of hot rolling is preferably 350-500 ℃. After the hot rolling, usually further carry out cold rolling. Before cold rolling, afterwards or during cold rolling, can also carry out the tough processing of centre refining. The tough processing of middle refining can be refined tough heating furnace with batch-type and carried out, and in this case, usually with ingot bar 280-600 ℃ of lower heating 2-20 hour, be desirable in 2-10 hour 350-500 ℃ of lower heating. The tough processing of middle refining can also be refined tough heating furnace with continous way and carried out, and in this case, usually with ingot bar 400-600 ℃ of lower heating 360 seconds or shorter, 450-540 ℃ of lower heating 120 seconds or shorter be desirable. It is preferred using continous way to refine tough heating furnace heating ingot bar under 10 ℃/second or longer condition, because the crystal structure in the gained moulding article is become more meticulous. When crystal structure can obtain becoming more meticulous, can not carry out the tough processing of centre refining in hot rolling. By cold rolling, finally obtain the aluminium alloy version of 0.1-0.5mm thickness. When by means for correcting such as roller leveler, tension leveler etc. the aluminium alloy version of gained being further processed, the flatness of aluminium alloy version will preferably be improved. In addition, when the width requirement of version reaches the width of regulation, can it be controlled to the width of regulation by the slitter line.

When the molten bath of direct casting aluminium alloy, obtain to have the version body of specific thickness, for example, allow the molten bath of aluminium alloy between a pair of biobelt or two roller, pass through. In by the aluminium alloy version body that uses biobelt thickness, can also further reduce thickness by the hot rolling machine. After hot rolling, can also be next by cold rolling reduction thickness. Afterwards, can be by heat treatment or by further process the version body with means for correcting if need. In by the version body that uses two roller thickness, can just reduce thickness by cold rolling machine from beginning, and not carry out hot rolling subsequently. If need, can further carry out the tough and correction of centre refining.

In cold-rolled process or trimming process, preferably make the reverse side (providing the opposite face of the side of photosensitive layer) of aluminium alloy version have certain average surface roughness. In cold-rolled process, can by with the design transfer of the Rolling roller reverse side to aluminium alloy, make the reverse side of aluminium alloy have above-mentioned average surface roughness. Equally, in trimming process, can have by use the roller of the pattern corresponding with the regulation surface roughness, with the reverse side of design transfer to substrate. In said method, set up certain average surface roughness and be preferred, because do not need to be arranged in addition the process such as roughening processing etc. of carrying out on the reverse side, and can simplify technology. For example, can wherein carry out cold rolling or similar processing along the roller of the average surface roughness of the roller direction of rotation pattern not identical with the average surface roughness of roller direction of rotation vertical direction with the edge by use, cause vertical average surface roughness of substrate reverse side from laterally average surface roughness is different.

Figure 1A and Figure 1B have shown the skeleton view of one embodiment of the invention and the reverse side of substrate.

The formation of lithographic plate presoma 40 comprises substrate 42 and is arranged on the type of directly writing photographic layer 14 on the surperficial 42a of substrate 42.On the reverse side 42b of substrate 42, in its both sides from the width d of side (1mm≤d≤50mm) longitudinally carry out slight surface treatment in the zone, shown in Figure 1B with the form of band.On the surperficial 42a of substrate 42, carry out roughened and anodization, make more closely contact between photographic layer 14 and the substrate 42 thus.

Figure 1B has shown an example, wherein in two side end offices of the reverse side 42b both sides of substrate 42 longitudinally (the x direction among the figure) carry out slight surface roughening and handle.Yet the present invention is not only limited to this configuration.For example, can be only vertically carry out slight roughened along reverse side 42b in the width d zone of side in a side.Equally, the slight roughened of carrying out band forms along laterally (the y direction the figure) in one or both sides in the width d zone of side also allows.

In the lithographic plate presoma of the present embodiment, because at least one side of substrate reverse side is in the slight roughened of quilt in the certain width of side, presoma is being transferred in each process of being undertaken by the user by conveying belt or conveying roller, can taking place such as troubles such as slip, conveying failures such as laser explosure, development, printing etc.On the substrate reverse side, be 1mm or to 50mm or littler zone, longitudinally or laterally carry out slight roughened greatlyyer at width from a side or two side ends.When width during less than 1mm, can not expect to reach the effect of anti-sliding stop, and width to surpass 50mm be not preferred economically become complicated because not only be used for the equipment of reverse side roughening like this, and the expense of roughening will increase.Here, " slight roughening " is meant the roughened of milder state, at least than the roughened gentleness of positive (forming the side of photographic layer).That is to say, be roughened the average surface roughness of the average surface roughness in zone on the reverse side less than the front that is roughened.By the zone that slight roughened is crossed, its average surface roughness (Ra) is preferably 0.15 μ m or bigger and 0.50 μ m or littler.From the viewpoint that prevents that photographic layer 14 is scratched when the lithographic plate presoma is rolled and deposited or pile up with drum forms and packs, the average surface roughness (Ra) in the zone that the slight roughened of quilt is crossed is preferably 0.15 μ m or bigger to 0.40 μ m or littler.

Next, the aluminium alloy version that obtains by above-mentioned technology is carried out roughened, comprise electrochemical rougheningization, be used as the substrate of lithographic plate presoma then.In the present invention,, therefore uniform electrochemical roughening processing can be carried out, and more closely contact between photographic layer and the substrate can be further made owing to contain the above-mentioned trace element of specified rate in the aluminium alloy.The electrochemical roughening processing of substrate can effectively be strengthened contacting with the tight of photographic layer, this is can form tiny degree of irregularity because handle on substrate surface, in the present invention specifically, owing to evenly form tiny degree of irregularity by adding trace element, further improved with the tight of photographic layer contacting.And then, when lithographic plate presoma of the present invention is applied to write type lithographic plate presoma when (being used for laser printing), can strengthen the tight contact between photographic layer and the substrate.Specifically, can solve distinctive problem in the direct description type lithographic plate presoma, as halation and exposure failure.

As a rule, the thickness that is used for the aluminium alloy substrate of substrate of the present invention is approximately 0.1-0.6mm.This thickness can change aptly according to the size of printer, the size and the requirement of galley.

For obtaining aluminium substrate, can further implement various surface treatments to this aluminium plate.Sand streakization

Obtain preferred form by sand streak processing aluminium plate.The sand streak disposal route is just like disclosed mechanical sand streakization, chemical etching, electrolysis veining etc. among the JP-A56-28893.In addition, can use galvanochemistry sand streak method in hydrochloric acid or nitric acid electrolyte, to carry out, can also use mechanical sand streak method such as wire brush veining method, wherein by the tinsel aluminium plate surface of swiping; Mill line method wherein makes the aluminium plate surface texturizing by mill ball and lapping compound; Brush line method wherein makes surface texturizing by nylon bruss and lapping compound.These sand streak methods can be used separately also and can be used in combination.

In said method, the method that can be used for acquisition substrate surface sand streakization of the present invention is an electrochemical method, and wherein sand streakization carry out in chemical ground in hydrochloric acid or nitric acid electrolyte, and suitable current density is 50-400C/dm at the anode place ²The electric weight scope.Say that more specifically this method is carried out under 20-100 ℃ of condition in the electrolyte that contains 0.1-50% hydrochloric acid or nitric acid, the processing time is that 1 second to 30 minutes and current density are 50-400C/dm ², use direct current or alternating current.Electrochemical rougheningization also is important to the tight contact that improves between photographic layer and the substrate, and this is because bring tiny degree of irregularity to substrate surface easily.

Carrying out roughened by this sand streak processing, can the area with 30-100% serve as the weld bond of about 0.5-20 μ m or the pit of honeycomb style than producing mean diameter on the aluminium plate surface.The ability that pit can effectively improve the duplicate printing of anti-colouring power and anti-non-image part is set here.

In the electrochemical roughening processing, provide enough pits to need enough electric weight for the aluminium plate surface, i.e. generation of electric current and the time span that applies electric current are the essential condition of electrochemical rougheningization.From saving the viewpoint of ability, also expectation forms enough pits with less electric weight.Surface roughness Ra after the roughened is preferably 0.2-0.5 μ m.Etch processes

By acid or alkali the aluminium plate through the sand streak processing is carried out further chemical etching.When using acid, decompose fine texture and need the long time as etchant.This is the weakness of the present invention in commercial Application.Yet this problem can be improved as etchant by using alkali.

Be suitable for the alkaline agent of etch processes of the present invention, for example can list NaOH, sodium carbonate, sodium aluminate, sodium silicate, sodium phosphate, potassium hydroxide, lithium hydroxide or the like.When using these alkaline agents to carry out etching, preferred concentration and temperature are respectively 1-50% and 20-100 ℃, and the preferred wherein meltage of aluminium is 5-20g/m ³Condition.

Carry out pickling and after removing etching, remain in the lip-deep pollution of aluminium plate (stain).The acid that is used for this purpose can be nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluorite, boron hydrofluorite or the like.Specifically, remove disposal route, can list the method for describing among the JP-A 53-12739 for example, allow the surface under 50-90 ℃, contact with the sulfuric acid of 15-65wt% as the stain after the electrochemical roughening processing; And the method for describing among the JP-B 48-28123, carry out alkaline etching.Anodization

Aluminium plate through above-mentioned processing is further carried out anodization.Anodization can be carried out according to the conventional method of this area.Specifically, when applying direct current or alternating current for the aluminium that is present in aqueous solution or the water-free solution, can form anodic film on the surface of aluminium plate, wherein said solution separately or be used in combination sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfaminic acid, benzene sulfonic acid etc.In this case, can certainly contain the component that at least often is contained in aluminium alloy version, electrode, tap water, the underground water etc. in the electrolyte.In addition, also can contain the second and the 3rd component.Here the said second and the 3rd component for example is the ion such as metals such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn; Kation such as ammonium ion etc.; Negative ion such as nitrate ion, carbanion, chlorion, phosphate anion, fluorine ion, sulfite ion, titanate radical ion, silicate ion, borate ion etc.; And other component, and its concentration can be 0-10000ppm.Although anodized condition is not done general decision because it is according to used electrolyte and difference, as a rule electrolytical concentration be 1-80%, liquid temperature for-5 to 70 ℃, current density be 0.5-60A/dm ², voltage is that 1-100V and electrolysis time suit for 10-200 second.

Among these anodization,, under high current density, in electrolyte sulfuric acid, carry out anodized method described in 768 preferably as GB patent 1,412.

In the present invention, the amount of formed anodic film is generally 1-10g/m ²When this is measured less than 1g/m ²The time, version is not easy to be scratched.When surpassing 10g/m ²The time, then for producing the electric energy that it must want enormous amount, have the sense of lacking economically.The amount of anodic film is preferably 1.5-7g/m ², more preferably 2-5g/m ²The surface area control and treatment

After anodization, preferably carry out the surface area of substrate is increased to the long-pending 2-30 of apparent surface processing doubly.The long-pending implication here of apparent surface is, is in the situation of 100mm * 100mm in galley, and when only roughened and anodization being carried out in a surface, apparent surface is long-pending to be 10000mm ², and all being roughened when all being used to print when two faces with anodization and two faces, apparent surface is long-pending to be 20000mm ²

Surface area can be measured by using gas absorption amount from the teeth outwards.Among the present invention, by the value that the supposition physisorption comes the reckoner area, said supposition physisorption is derived by the adsorbance of using Kanta Sorb (trade name, the Yuasa Ionics makes) helium of measuring and the fixed gas of 0.1% krypton.

The most popular method that makes surface area reach desirable value is that pass through pressurized water steam and the hot water antianode film described among JP-A 4-176690 and the JP-A 10-106819 carry out the micropore sealing and handle, and above-mentioned two pieces of patents are proposed by the present inventor.

In addition, can also be undertaken by using known method, for example silicate processing, the processing of dichromate aqueous solution, nitrite treatments, the processing of acetate ammonium salt, the sealing of electro-deposition micropore are handled, triethanolamine is handled, barium carbonate is handled, use contains phosphatic hot water treatment of minute quantity or the like.For example, when carrying out electro-deposition micropore sealing processing from the bottom in hole, form the film of micropore sealing.In this case, because the degree of depth of micropore is controlled, thereby stoped the absorption of infrared absorbing agents and the further portion that the photographic layer material is invaded micropore, the latter can cause the mobility of photographic layer poor.Therefore, the inhibition effect of film reservation is outstanding.When carrying out water vapor micropore sealing processing, film forms from the top of micropore.In this case, owing to form the gap in the substrate, thermal insulation properties is improved.As mentioned above, the embodiment that forms closing membrane depends on mode that the micropore sealing is handled and difference.As long as the final substrate that obtains satisfies the surface area of regulation, can handle the purpose that is provided according to the micropore sealing and select any micropore sealing to handle.

In addition, can control the method for the micropore degree of depth and size to surface applied.As long as can with surface area control within the limits prescribed method not done special restriction, for example, can select solution infiltration processing, spray treatment, coating processing, deposition processes, sputter process, ion plating, thermal spray, spraying plating or the like.But the method for control table area is not done concrete restriction.

As particular treatment method, cited method is to be used for providing the disclosed layer of being made up of compound as JP-A 60-19491 according to rubbing method, and wherein said compound contains at least one amino and at least one is selected from the group of carboxyl and salt and sulfo group and salt thereof; As the disclosed layer of being made up of compound among the JP-A 60-232998, wherein said compound is selected from and contains at least one compound and salt thereof amino and at least one hydroxyl; As disclosed phosphatic layer among the JP-A 62-19494; As the disclosed layer of being made up of polymkeric substance among the JP-A 59-101651, wherein said compound contains at least one monomeric unit that contains sulfo group as repetitive or the like.

The method of the layer that contains compound is provided in addition, and said compound is selected from carboxymethyl cellulose; Dextrin; Gum arabic; Contain amino phosphonic acids, as 2-amino-ethyl phosphonic acids or the like; Organic phospho acid as phenyl-phosphonic acid, naphthyl phosphonic acids, alkyl phosphonic acid, glycerine phosphonic acids, methylenediphosphonate and ethylidene diphosphonic acid or the like, optionally has substituting group on every kind; Organic phosphate as phosphenylic acid, naphthyl phosphoric acid, alkyl phosphoric acid, phosphoglycerol or the like, optionally has substituting group on every kind; Organic phosphinic acids as phenyl phosphinic acid, naphthyl phosphinic acids, alkyl phosphinic acid, glycerine phosphinic acids etc., optionally have substituting group on every kind; Amino acid, for example glycocoll, beta Alanine etc.; And the hydrochloride with amine of hydroxyl, as hydrochloride of triethanolamine or the like.

In addition, can use silane coupling agent, and the example of operable silane coupling agent comprises N-(3-acryloxy 2-hydroxypropyl)-3-aminopropyltriethoxywerene werene with unsaturated group, (3-acryloxy propyl group) dimethyl methyl TMOS, (3-acryloxy propyl group) methyl dimethoxysilane, (3-acryloxy propyl group) trimethoxy silane, 3-(N-allyl amino) propyl trimethoxy silicane, the allyl dimethyl TMOS, allyltriethoxysilane, allyltrimethoxysilanis, 3-butenyl group triethoxysilane, 2-(chloromethyl) allyl methoxy silane, the Methacrylamide propyl-triethoxysilicane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene, (methacryloxy methyl) dimethylethoxysilane, the methacryloxy methyl triethoxysilane, the methacryloxy methyltrimethoxy silane, the methacryloxypropyl dimethylethoxysilane, methacryl propyl-dimethyl methoxy silane, the methacryloxypropyl methyldiethoxysilane, the methacryloxypropyl methyl dimethoxysilane, the methacryloxypropyl methyl triethoxysilane, the methacryloxypropyl methyltrimethoxy silane, methacryloxypropyl three (methoxy ethoxy) silane, methoxyl diethyl vinyl silanes, 1-methoxyl-3-(trimethylsiloxy) butadiene, the styryl ethyl trimethoxy silane, 3-(N-styryl methyl 2-aminoethylamino)-propyl trimethoxy silicane hydrochloride, vinyl-dimethyl base oxethyl silane, vinyl diphenyl Ethoxysilane, the vinyl methyldiethoxysilane, the vinyl methyl dimethoxysilane, neighbour-(vinyl oxygen base ethyl)-N-(triethoxysilylpropyltetrasulfide) urethane, vinyltriethoxysilane, vinyl trimethylsilane, vinyl three tert-butoxy silane, the vinyl tri isopropyl silane, vinyl triple phenoxyl silane, vinyl three (2-methoxy ethoxy) silane and diallyl aminopropyl methoxy silane.Wherein, the coupling agent that contains methacryl and acryloyl group (wherein the reactivity of unsaturated group is fast) is preferred, and can be allowed to the vinyl of unsaturated group and allyl are provided be dual functional.

In addition, can also use the sol-gel coating described in JP-A 5-50779 to handle; Phosphonic acids coating described in JP-A5-246171 is handled; Described in JP-A 6-234284,6-191173 and 6-230563, be coated with the method for material coating surface with the back of the body; Phosphonic acids described in the JP-A 6-262872 is handled; Coating shown in the JP-A6-297875 is handled; Cause anodized method shown in the JP-A10-109480; In addition, the dip treating method described in JP patented claim 10-252078 and the 10-253411, these two pieces of patents propose for the present inventor.

Treatment conditions preferably are chosen as after anodization, by said method, anodic film has following characteristics, and for example (a) surface area is a 2-30 times of per surface area, and/or the aperture of the micropore that (b) exists in the anodic film is 5-10nm, and hole density is 8 * 10 ¹⁵-2 * 10 ¹⁶/ m ²For the control table area in required scope, must to control the type and the treatment conditions of used treating agent.For example, can control the micropore sealing processing of carrying out with pressure (hydraulic) water steam or hot water by the temperature and/or the processing time that change water vapor or hot water.In addition, in the dip treating of using aqueous solution, can be by changing concentration, treatment temperature and the processing time control table area of solute.In electro-deposition micropore deposition processes,, can also come the control table area by current density, decomposition voltage and the electrolysis waveform in the control electro-deposition except that control electrolyte concentration, treatment temperature with the processing time.On the other hand, when controlling, can come control surface by change coating weight, the molecular weight that is coated with the compound of usefulness, drying condition (as temperature, time, heating means), the coating process (rod is coated with method, extraction, spin rubbing method etc.) after the coating by the coating processing.Photographic layer

Next on the substrate of the present invention of above-mentioned production, form imaging layer.The used imaging layer of the present invention can provide by the infrared laser irradiation to be write, but does not do concrete restriction.This photographic layer can pass through exposure and give infrared laser and direct record thereon, and is exposed the solubleness change of part in alkaline development solution, below it is called the pattern of fever photographic layer for simplicity.

Directly write type pattern of fever photographic layer as the laser that is used for lithographic plate and can use conventional known layer.For example be described in JP-A 9-222737,9-90610,9-87245,9-43845,7-306528 and by the photographic layer of describing among the present patent application people disclosed JP patented claim 10-229099 and the 11-240601, recording layer or the like.

Contain infrared absorbing agents, water insoluble and be dissolved in polymkeric substance and other selectable component of alkaline aqueous solution in this pattern of fever photographic layer.By such as the key of cancelling cambial polymkeric substance with the heat energy itself of acid or rayed and heating generation, positive recording layer is dissolved in water and the alkaline aqueous solution.Then, remove layer, form non-image part by development.In negative layer, by using acid that free radical or rayed and/or heating produce, make the compound polymerization and/or the crosslinked and sclerosis that constitute recording layer as initiating agent or catalyzer, form image section.

In the present invention, for simplicity polymkeric substance water insoluble and that be dissolved in alkaline aqueous solution be called for short is done " dissolving in the polymkeric substance of alkaline aqueous solution ".

As this polymkeric substance, preferred homopolymer, its multipolymer or its potpourri that in the main chain of polymkeric substance and/or side chain, contains acidic-group that use.

Wherein, from the viewpoint of solubleness alkaline development solution and proof solution inhibition ability, the polymkeric substance of enumerating in preferably following (1)-(6) that in main polymer chain and/or side chain, has acidic-group.(1) phenolic groups (the Ar-OH) (SO of (2) sulfonamido group ₂NH-R) (3) substituted sulfonamides acid groups (after this being called " active imide group ") (4) carboxyl (CO ₂H) (5) sulfo group (SO ₃H) (6) bound phosphate groups (OPO ₃H ₂)

In above-mentioned (1)-(6), Ar represents the divalent aryl linking group, and selectivity has substituting group on it, and R represents that alternative has substituent hydrocarbyl group.

In being selected from the polymkeric substance that dissolves in alkaline aqueous solution with acidic-group of (1)-(6), for guaranteeing solubleness enough in alkaline development solution, development latitude and film strength, preferably have the polymkeric substance that dissolves in alkaline aqueous solution of (1) phenolic groups, (2) sulfonamido and (3) active imide group, and especially preferably have the polymkeric substance that dissolves in alkaline aqueous solution of (1) phenolic groups and (2) sulfonamido.

The polymkeric substance that dissolves in alkaline aqueous solution as having the group that is selected from above-mentioned (1)-(3) is listed below.

As the polymkeric substance that dissolves in alkaline aqueous solution with (1) phenolic groups, novolac resin is for example arranged, bunching compound as phenol and formaldehyde, the bunching compound of metacresol and formaldehyde, the bunching compound of paracresol and formaldehyde, between/the bunching compound of paracresol potpourri and formaldehyde, phenol, cresols (-, to or-/right-potpourri) and the bunching compound of formaldehyde or the like, and the bunching compound of pyrogallol and acetone.In addition, can also enumerate the multipolymer that obtains by the compound copolymerization that side chain is had phenolic groups.In addition, also can use the multipolymer that obtains by a kind of compound copolymerization that side chain is had phenolic groups.

As compound with phenolic groups, can be acrylamide, Methacrylamide, acrylate, methacrylate, hydroxy styrenes or the like, they all have phenolic groups.

From the viewpoint of imaging performance, preferable weight-average molecular weight is 5.0 * 10 ²-2.0 * 10 ⁴And number-average molecular weight is 2.0 * 10 ²-1.0 * 10 ⁴The polymkeric substance that dissolves in alkaline aqueous solution.These polymkeric substance can use separately also and can be used in combination.When being used in combination these polymkeric substance, can adding and use the bunching compound that has substituent phenol of 3-8 carbon atom alkyl and formaldehyde, as tert-butyl phenol and the bunching compound of formaldehyde and the bunching compound of describing in the US patent 4123279 of octyl phenol and formaldehyde.

As the polymkeric substance that dissolves in alkaline aqueous solution with sulfonamido (2), for example be the polymkeric substance that constitutes by the minimum component units that is obtained from compound with sulfonamido, wherein said unit is used as the main component that constitutes.Above-claimed cpd is the compound that contains one or more sulfonamidos and one or more polymerizable unsaturated groups in the molecule, and at least one hydrogen atom in the wherein said sulfonamido links to each other with nitrogen-atoms.Wherein, contain in the preferred molecule acryloyl group, allyl or vinyl oxygen base and replacement or single substituted-amino sulfonyl or replace the sulphonyl imino group than small molecular weight compounds.The compound of representing by following general formula 1-5 for example. Wherein X1 and X2 represent independently of one another-O-or-NR27-.R21 and R27 represent independently of one another hydrogen atom or-CH3.R22, R25, R29, R32 and R36 represent alkylidene, cyclic alkylidene, arlydene or aryl alkylene independently of one another, have the 1-12 carbon atom separately and optionally have substituting group.R23, R27 and R33 represent hydrogen atom, alkyl, naphthenic base, aryl or aralkyl independently of one another, have the 1-12 carbon atom separately and optionally have substituting group.R26 and R37 represent alkyl, naphthenic base, aryl or aralkyl independently of one another, have the 1-12 carbon atom separately and optionally have substituting group.R28, R30 and R34 represent independently of one another hydrogen atom or-CH3.R31 and R35 represent singly-bound or alkylidene, cyclic alkylidene, arlydene or aryl alkylene independently of one another, have the 1-12 carbon atom separately and optionally have substituting group.Y3 and Y4 represent separately to represent independently singly-bound or-CO-.

In the compound that general formula 1-5 represents, amino-sulfonyl phenylester, N-(to the amino-sulfonyl phenyl) Methacrylamide, N-(to the amino-sulfonyl phenyl) acrylamide or the like are suitable to planographic printing plate material of the present invention between methacrylic acid specifically.

As the polymkeric substance that dissolves in alkaline aqueous solution with active imide group (3), for example be the polymkeric substance that constitutes by the minimum component units that is obtained from compound with active imide group, wherein said unit is used as the main component that constitutes.Above-claimed cpd is the compound that contains one or more active imide groups and one or more polymerizable unsaturated groups in the molecule, and wherein said active imide group is represented by following structural formula.

Specifically, N-(p-toluenesulfonyl) Methacrylamide, N-(p-toluenesulfonyl) acrylamide or the like can use aptly.

The minimum polymkeric substance that dissolves in alkaline aqueous solution, that have the acidic-group that is selected from above-mentioned (1)-(6) that is configured for the positive recording layer of the present invention constitutes the unit, and particular requirement is not used separately.Also can use the polymkeric substance that obtain by with the unit copolymerization of two or more minimum formation, wherein said two or more minimum formations unit can have identical acidic-group or have different acidic-groups.

As copolymerization process, can use conventional known method, as grafting copolymerization process, the disconnected copolymerization method of embedding, random copolymerization method or the like.

As above-mentioned multipolymer, contain in the preferred copolymer 10mol% or have be selected from (the compound of 10-(6) acidic-group, and more preferably contain 20mol% or have a compound that is selected from (1)-(6) acidic-group more.When the content of compound during, cause easily and can not enough improve development latitude less than 10mol%.

As the preferred polymers that can be used for negative image forming material recording layer, can be the polymkeric substance that on its side chain or main chain, has the aromatic hydrocarbon ring, wherein directly be connected with hydroxyl or alkoxy on the aromatic hydrocarbon ring.As alkoxy,, preferably have 20 carbon atoms or still less from the viewpoint of sensitivity.As the aromatic hydrocarbon ring, from the preferred phenyl ring of the availability of raw material, naphthalene nucleus or anthracene nucleus.Can have the substituting group except hydroxyl or the alkoxy on these aromatic hydrocarbon rings, as halogeno-group, cyano group or the like.Yet from the viewpoint of sensitivity, preferred ring goes up hydroxyl-removal or alkoxy does not contain substituting group outward.

Have by the polymkeric substance that constitutes the unit shown in the following general formula (III) during the suitable binder polymer that uses in the present invention, or such as the phenol resin of novolac resin etc.

In the formula, AR ²Expression phenyl ring, naphthalene nucleus or anthracene nucleus.R ⁴Expression hydrogen atom or methyl.R ⁵Expression hydrogen atom or 20 carbon atoms or the alkoxy of carbon atom still less.X ¹Expression singly-bound or divalent linker contain the one or more atoms that are selected from C, H, N, O and S and have 0-20 carbon atom in this divalent linker.K represents the integer of 1-4.

Below be to be suitable for the example ([BP-1] is to [BP-6]) by the unit of formation shown in the general formula (III) of the present invention.Yet the present invention is not restricted to this.

Having these polymkeric substance that constitute the unit can use their corresponding monomers by the incompatible acquisition of radical polymerization according to the known method of routine.

Next novolac resin is described.As being suitable for novolac resin of the present invention, can be phenol type novolac resin, adjacent-,, to type various cresols type novolac resin and multipolymer thereof, the phenol that is substituted with halogen atom, alkyl or the like by use obtains novolac resin.

The weight-average molecular weight of these novolac resins is preferably 1000 or higher, and more preferably 2000-20000, and number-average molecular weight is preferably 1000 or higher, more preferably 2000-15000.The polydispersion degree is preferably 1 or higher, more preferably 1.1-10.

Infrared absorbing agents contained in the recording layer of the present invention has the ability that the infrared ray that will be absorbed is transformed into heat, and causes photochemical reaction or the like by laser scanning, obviously improves the solubleness of recording layer in developing solution thus.

Used infrared absorbing agents is effectively to absorb ultrared dyestuff of 760-1200nm wavelength or pigment among the present invention, and preferably its absorption maximal value is the dyestuff or the pigment of 760-1200nm wavelength coverage.

As dyestuff, can use the known dye of describing in the dyestuff of commercially available acquisition and the document, for example " Senryo Binran (dyestuff handbook) " (Yuki Gosei Kagaku Kyokai edits 1970) or the like.Specifically, said dyestuff has azo dyes, metallic complex salt azo dyes, pyrazoline azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dyestuff, quinoneimine dye, methine dyes, cyanine dye, the husky salt dyestuff in angle, pyrans, metal thiolate complex compound or the like.

As being used for pigment of the present invention, can use commercially available acquisition pigment and be described in ＂ color index (Color Index (C.I.)) handbook, (Niho Gnaryo GijutsuKyokai edits ＂ Saishin Gnaryo Binran (dyestuff handbook) ＂, 1977), (CMC publishes ＂ Saishin Ganryo Oyo Gijutsu (new pigment applications technology) ＂, 1986), the pigment of describing among ＂ Insatsu Inki Gijutse (printing-ink technology) ＂ (CMC publishes, 1984).

Can use any of these infrared absorbing agents, as long as it has photo-thermal transformation function under non-exposure wavelength, and specifically for example by the inventor at JP-A 11-985, the absorbing agent of describing in [0038]-[0050] can use aptly.

The addition of dyestuff or pigment is preferably about 0.01-30wt% of recording layer coating solution total solids content.

In addition, the negative ion infrared absorbing agents of describing among the JP patented claim 10-237634 is the example that suits.

The polymkeric substance that dissolves in alkaline aqueous solution for reduction is exposed alkaline aqueous solution solubleness partly, allowing negative recording layer contain can be by light or acidic acid agent of thermal decomposition and acid crosslinking agent, wherein said acid crosslinking agent can be caused cross-linking reaction by the acid that is produced, with the curing adhesive polymkeric substance or can produce the compound of free radical and the sour polymerization that can be produced and the compound of sclerosis by light or heat.

In recording layer of the present invention, except that using above-claimed cpd, various known additives can be used with above-claimed cpd if desired.

Lithographic plate presoma of the present invention by with these compound dissolutions in The suitable solvent with the preparation photosensitive layer coating solution and it is coated on the aluminium substrate with above-mentioned specific surface area obtains.

The coating weight of recording layer (solid constituent) depends on use and difference among the present invention, and is controlled at 0.01-2.0g/m ²

As coating process, can make in all sorts of ways.For example excellent coating machine coating, rotary coating, spraying, curtain type coating, dip-coating, air doctor blade, the coating of version sheet, print roll coating or the like.When coating weight reduced, apparent sensitivity increased, and the film properties of photographic layer descends.

Photosensitive printed board presoma for the scattered light that obtains to be not easy to be belonged to substrate makes the chap of medium tone point preferably provides the photographic layer with following characteristics on the substrate of the anodic film with These characteristics (b).

In this case, preferred photographic layer contains (ⅰ) at least a cyclopentadiene titanium compound, (ⅱ) but has the compound and (ⅲ) pigment of penetrability is littler than penetrability under the 400nm under at least a 500nm of having optical property of the addition polymerization of at least one alkene formula unsaturated double-bond.(ⅰ) cyclopentadiene titanium compound

As cyclopentadiene titanium compound contained in the photographic layer of the present invention, can allow any cyclopentadiene titanium compound, as long as it can produce active substance on request when the common existence of described photosensitive pigment is descended with rayed in the back.As this cyclopentadiene titanium compound, the suitable selection and use when for example being described in the known compound among JP-A 59-152396,61-151197,63-41483,63-41484,2-249,2-291,3-27393,3-12403 and the 6-41170.

More specifically say, dicyclopentadienyl-Ti-dichloride is arranged, dicyclopentadienyl-Ti-diphenyl, dicyclopentadienyl-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, dicyclopentadienyl-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, dicyclopentadienyl-Ti-two-2, and 4,6-trifluoro-benzene-1-base, dicyclopentadienyl-Ti-two-2,6-two fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4-two fluorobenzene-1-base, dimethyl cyclopentadienyl group-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, dimethyl cyclopentadienyl group-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, dimethyl cyclopentadienyl group-Ti-two-2,4-two fluorobenzene-1-base, two (cyclopentadienyl group)-two (2,6-two fluoro-3-(pyrans-1-yl) phenyl) titanium or the like.

In addition, can carry out various chemical modifications to these cyclopentadiene titanium compounds and handle, to improve the performance of photographic layer.But for example can be in conjunction with unsaturated compound or other activator part of following photosensitive pigment addition polymerization; Introduce hydrophobic position; The substituting group that introducing is used to improve compatibility and suppresses crystal deposition; Introducing is used to improve the substituting group that closely contacts between substrate and the photographic layer; Polymkeric substance forms or the like.

And, can set the use of said method by the ability that design sensitive offset press version is desired to think aptly.For example, can strengthen compatibility with photographic layer etc. by the compound that uses two or more simultaneously.From the viewpoint of light sensitivity, the use amount height of cyclopentadiene titanium compound is normally favourable.Total component based on above-mentioned photographic layer etc. is 100 weight portions, obtains enough light sensitivity by the cyclopentadiene titanium compound that uses 0.5-80 weight portion, preferred 1-50 weight portion.On the other hand, when using under the condition that at wavelength is the light of about 500nm such as white lamps, amber light etc., from the viewpoint of photographic fog, preferred use amount is less.Even its use amount is reduced to 6 weight portions or still less, even 1.9 weight portions, even 1.4 weight portions or still less, by being used in combination the light sensitivity that cyclopentadienyltitanium and following photosensitive pigment strengthen light initiation system, still can obtain enough light sensitivity.But the compound that (ⅱ) has the addition polymerization of at least one alkene formula unsaturated double-bond

Next, but illustrate the compound (after this, but can be called the compound of addition polymerization) of addition polymerization contained in the photographic layer of the present invention with at least one alkene formula unsaturated double-bond.

But the compound of the addition polymerization that photographic layer is contained be selected from have at least one, the compound of preferred two or more alkene formula unsaturated link end groups.These compounds are well known in the art, and can not be subjected to specifically restrictedly to be used for the present invention.Their chemical species is for example monomer, prepolymer (being dipolymer, trimer and oligomer), its potpourri, its multipolymer or the like.The example of monomer and multipolymer is unsaturated carboxylic acid (as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and ester and acid amides, and preferably uses the ester of unsaturated carboxylic acid and aliphatic polyol compound and the acid amides of unsaturated fatty acid and aliphatic multivalence amines.In addition, can also use aptly and have hydroxyl and such as the unsaturated carboxylic acid of nucleophilic displacement of fluorine bases such as amino, sulfydryl; The addition compound product of acid amides and simple function or polyfunctional isocyanate or epoxy compound; With dehydration condensation reaction products of simple function or polyfunctional carboxylic acids or the like.

In addition, has isocyanide acyl group and such as the electric substituent esters of unsaturated carboxylic acids of parent such as epoxide group; The addition compound product of acid amides and simple function or polyfunctional alcohol, amine and mercaptan; But the esters of unsaturated carboxylic acids that contains halo group and release property substituting group such as tosyl oxygen base; The substitution product of acid amides and simple function or polyfunctional alcohol, amine and mercaptan also suits.As other example, the compound that can also use above-mentioned unsaturated carboxylic acid to be replaced by unsaturated phosphonic acids, styrene, vinyl ether etc.

The instantiation of the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid comprises acrylate, as ethylene glycol diacrylate, the diacrylate triglycol ester, diacrylate 1, the 3-butanediol ester, diacrylate tetramethylene glycol ester, the diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyl group oxygen base propyl group) ether, the trimethylolethane acrylate, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acryloyl group oxygen base ethyl) chlorinated isocyanurates, polyester acrylic ester oligomer or the like;

Methacrylate, as dimethacrylate tetramethylene glycol ester, the dimethacrylate triglycol ester, the dimethacrylate DOPCP, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, Ethylene glycol dimethacrylate, dimethacrylate 1,3 butylene glycol ester, dimethacrylate hexanediol ester, the dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, dimethacrylate two [right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] ester, dimethacrylate two [right-(methacryloxy ethoxy) phenyl] ester or the like;

Itaconate, as two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acid 1,3 butylene glycol esters, two itaconic acids 1,4-butanediol ester, two itaconic acid tetramethylene glycol esters, two itaconic acid pentaerythritol esters, four itaconic acid sorbitol esters or the like;

Crotonates is as two crotonic acid glycol esters, two crotonic acid tetramethylene glycol esters, two crotonic acid pentaerythritol esters, four crotonic acid sorbitol esters or the like;

The iso-crotonic acid ester is as two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters, four iso-crotonic acid sorbitol esters or the like;

Maleate is as two maleic acid glycol esters, two maleic acid triglycol esters, two maleic acid pentaerythritol esters, four maleic acid sorbitol esters or the like.

As other example of ester, the aliphatic alcohol esters that suitable use is for example described among JP-B 46-27926,51-47334, the JP-A 57-196231; The ester of describing among JP-A 59-5240,59-5241 and the 2-226149 with aromatics skeleton; Ester that contains amino of describing among the JP-A 1-165613 or the like.

In addition, can use the potpourri of above-mentioned ester monomer.

The instantiation that is obtained the monomer of acid amides by aliphatic polyamine and unsaturated carboxylic acid comprises methylene diacrylamine, methylene DMAA, 1,6-hexa-methylene diacrylamine, 1,6-hexa-methylene DMAA, diethylene triamine three acryloyls are by, xylylene diacrylamine, xylylene DMAA or the like.

As other example of preferred amide monomer, enumerate the acid amides of describing among the JP-B 54-21726 with ring-type hexylidene structure.

But by using the isocyanates and the compound of the urethanes addition polymerization of the addition reaction acquisition of hydroxyl also to suit.Its concrete example comprises the vinyl urethane compounds that contains two or more polymerisable vinyl in the molecule for example, the vinyl monomer that adds the hydroxyl shown in the following formula (I) by the polyisocyanate compounds that has two or more isocyanate groups in molecule obtains, as described in JP-B48-41708.

CH ₂=C (R) COOCH ₂CH (R ＇) OH formula (I)

Wherein R and R ' expression H or CH ₃

In addition, the urethane compounds of describing among the urethane acrylate of describing among JP-A 51-37193, JP-B2-32293 and the 2-16765 and JP-N 58-49860,56-17654,62-39417 and the 62-39418 with oxirane skeleton also suits.

In addition, but the photosensitive composition by using the compound that has the addition polymerization of amino structure or sulfide structure in the molecule can obtain to have extremely outstanding film speed, as described in JP-A 63-377653,63-260909 and 1-105238.

In addition, can use polyfunctional acrylic ester and methacrylate, as the polyester acrylate of describing among JP-B 48-64183,49-43191 and the 52-30490; By epoxy resin is reacted epoxy acrylate that obtains or the like with (methyl) acrylic acid.In addition, can enumerate the specific unsaturated compound of describing among JP-B46-43946,1-40337 and the 1-40336; Vinyl phosphonic acid compounds of describing among the JP-A 2-25493 or the like.In some cases, the suitable structure of using as describing among the JP-A 61-22048 that contains perfluoroalkyl.In addition, can also use Nippon Secchaku Kyokai Shi (Japanese bonding agent research institute magazine) vol.20, No.7, the material among the pp300-308 (1984) is introduced as photo-hardening monomer and oligomer.

But the details of the using method of the compound of addition polymerization, the amount of using or using jointly and add as the type of used structure, separately is to desire to want that according to sensitive offset press version presoma the ability that designs sets aptly.For example select details according to following viewpoint.From the viewpoint of film speed, have the structure of big content unsaturated group in the preferred per molecule, and in a lot of situations, preferred difunctionality or more polyfunctional structure.For increasing the intensity of image section, it is cured film, preferred trifunctional or more polyfunctional structure are in addition by using compound (as acrylate, methacrylate, distyryl compound and vinyl ether compound) also effectively sense of control luminosity and the intensity with different functional number and different polymerizable groups simultaneously.From developing powder be deposited on viewpoint the developing solution, preferably do not have the compound of macromolecule sometimes and have bigger hydrophobic compound, although from the viewpoint of film speed and film strength they the time superior.In addition, for dispersibility and with photographic layer in the compatibility of other component (as binder polymer initiating agent, colorant or the like), but the compound of addition polymerization is selected and using method is a key factor.For example, can improve compatibility by using compound and additional two or more compounds that use in some cases than low-purity.In addition, contact with the tight of substrate, also can select the ad hoc structure of describing later such as seal coat or the like for improving photographic layer.But, be favourable from the higher ratio of the viewpoint of light sensitivity for the proportioning of addition polymerization compound.Yet, when ratio is too high, what can take place not expect be separated and the problem in process of production that the viscosity owing to photographic layer causes (for example shift owing to the sensitization component and the bonding production that causes is failed) may takes place and such as the problem that deposits in developing solution.For these viewpoints, preferred proportioning is the 5-80wt% of photographic layer component total amount in a lot of situations, preferred 25-75%.These can use separately also and can two or more be used in combination.But in the method for the compound that uses addition polymerization, can suppress that degree, resolution, photographic fog, index of refraction change according to the polymerization of oxygen, the tight viewpoint of contact or the like in surface, the structure of at random selecting to suit, suitable proportioning and the additive compound of Sq.In addition, in some cases, structure that can also execution level and as the coating process that is coated with of priming paint coating and polishing.(ⅲ) has the pigment of the optical property that penetrability is littler than penetrability under the 400nm under the 500nm

To illustrate the pigment with optical property that penetrability is littler than penetrability under the 400nm under the 500nm that can be included in the photographic layer of the present invention below.

In one aspect of the invention, can not limit use pigment, as long as it has the penetrability optical property littler than penetrability under the 400nm under the 500nm.The optical property of this pigment can be controlled by the suitable chemical constitution and the dispersion condition (grain graininess, diluting condition or the like) of the coloring material of formation pigment selected.In addition, use normally used spectrophotometer can easily check its optical property by the film and the employing light transmission measurement method that for example on optical transparent substrate, produce pigment dispersing.When dispersion membrane formed on opaque substrate, optical property can be determined as the inverse of index of refraction, and wherein index of refraction obtains by regular reflectometry and diffusion emission determination method.

To describe with the C.I. number described in ＂ color index (ColourIndex) ＂ (The Society of Dyes and Colurists publishes, the 3rd edition) below and be preferred for pigment of the present invention: azo dyes

For example

Orange pigment 13,16,2,24,31

Red pigment 1,22,3,38,4,48,49,60,63,9,166,144

Brown pigments 23 or the like.Flower pigment

For example

Orange pigment 7

Red pigment 123,178,179,224,149,190

Violet pigment 29 or the like.Pyrazolone quinazolone pigment

For example

Red pigment 251,252

Orange pigment 67 or the like.The amino anthraquinones dyestuff

For example

Red pigment 177 or the like.Quinacridone pigment

For example

Violet pigment 19

Red pigment 122,202 or the like.The acid dyes mordant pigment

For example

The basic dyestuff mordant pigment of blue pigment 61,56,57 or the like

For example

Violet pigment 1

Red pigment 81 or the like.Other pigment

For example

France ultramarine or the like.

When the coloring compound that constitutes pigment of the present invention with non-solid disperse state but when being present in the photographic layer, the adverse effect that increases or sharply descend such as photographic fog can take place with molecule disperse state (solution).Therefore, preferably make the alap pigment of this influence.From owing to the absorption spectrum performance of pigment component chemical constitution and the viewpoint of solubleness, suitable pigment is azo dyes, northern pigment, pyrazolone quinazolone pigment, pyrazolone quinazolone pigment, amino anthraquinones dyestuff, quinacridone pigment, acid dyes mordant pigment and basic dyestuff mordant pigment among the present invention.In addition, more preferably azo dyes, acid dyes mordant pigment, pyrazolone quinazolone pigment and quinacridone pigment.

The chemical structural formula of the coloring material of formation preferred pigments is as follows:

Next, the conventional method of dispersed color is described.Yet the invention is not restricted to these descriptions.

As a rule, pigment provides by drying after synthetic.Often be dried pigment and provide from aqueous medium as body of powder.Yet, because the drying of water needs huge evaporation potential, the essential next dry powder that obtains of big heat energy that needs.Therefore, pigment is often owing to the gathering of primary granule forms coalescent granule (secondary granule).

The pigment dispersing that forms the agglomerate particles body is become fine grained and be not easy.Therefore, preferably use various plastic resin treatment pigment in advance.Resin can be the described binder resin in back.Disposal route can be that flushing is handled, and uses kneader, extruder, ball milling, two roller or three-roll grinder or the like to mediate.Wherein, flushing is handled and is used two rollers or three-roll grinder to make fine grained and suits.

It is a kind of common method that flushing is handled, wherein the aqueous dispersions with pigment mixes with resin solution, wherein said resin solution by be dissolved in the immiscible solvent of water in prepare, pigment is extracted into from aqueous medium in the organic media, and uses plastic resin treatment pigment.According to this method, can prevent the coalescent of pigment, and disperse to become easy owing to the drying of not carrying out pigment makes.It is a kind of method with the mixed with resin in pigment and the resin solution that two rollers or three-roll grinder are mediated.Then, by with pigment with resin is kneaded together applies higher shearing (shearing force) simultaneously with resin-coated surface at pigment.Granules of pigments coalescent in this process is dispersed into primary granule by the agglomerate particles body from fewer magnitude.

In addition, the pigment of anticipating through processing with acryl resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like is favourable.Form with the processed pigment of above-mentioned various plastic resin treatment can be, powder type, paste form, ball shape form, and the preferred homodisperse paste form of resin and pigment wherein.The inhomogeneous large volume form that preferably obtains not by the gelling resin.

For obtaining to have the pigment dispersion that fine grained distributes, at first to mediate with binder resin and handle pigment by flushing or by kneader, extruder, ball milling, two roller or three-roll grinder.Preferred kneading method is at first solvent to be added in pigment and the binder resin, then with they even mixing, mediates by two rollers or three-roll grinder, heats in case of necessity, allows pigment and binder resin comply with each other, obtains band look object uniformly.Afterwards, itself and other are constituted component mixes, comprise pigment of the present invention and pigment dispersing agent, and with the wet dispersion of potpourri (elementary dispersion) of gained.Use thinner pearl that the dispersion rewetting of gained is disperseed (secondary dispersion), until obtaining desired particle size distribution.Perhaps, for the particle that acquisition has desired grain graininess and size-grade distribution, remove large-volume particulate by centrifuging or decant and separate wet dispersion of disperseing.Coexistence has tertiary amine compound in above-mentioned kneading process and dispersion process, and during for example as spreading agent, can promote pigment so that form more fine grain dispersion.This is favourable to obtaining to have particle size distribution of the present invention.Specifically, be preferably as follows described tertiary amine compound with at least one polymeric groups.Can use any group as at least one polymeric groups on the tertiary amine, precondition is that it is the group with at least one polymkeric substance.This polymeric groups is low-grade alkylidene oxygen base group preferably.Here polyoxyethylene and polyoxypropylene all are alkylidene oxygen base groups.Preferred in addition wherein polyoxyethylene and polyoxypropylene form the alkylidene oxygen base group of inlay and break copolymer.Can be on the tertiary amine in conjunction with any amount of this polymkeric substance.

In addition, for improving dispersing of pigments, can add conventional known pigment dispersing agent and surfactant.Spreading agent can use polytype compound, cationic surfactant for example, as phthalocyanine dye derivant (trade name: EFK-745, Morishita Sangyo K.K. manufacturing), organic siloxane polymer (trade name: KP-341, the manufacturing of Shine-Etsu chemistry company limited), (methyl) acrylic acid (being total to) polymkeric substance (trade name: Polyflow No.75, No.90, No.95, Kyoei sha Yushi Kagaku Kogyo manufacturing), W001 (trade name, Yusho K.K. makes) or the like; Non-ionic surfactant is as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, fatty acid esters of sorbitan or the like; Fluorochemical surfactant, as F Top EF 301, EF303, EF352 (trade name, Shin Akita Kasei manufacturing), Megak F171, F172, F173 (trade name, Dainippon Ink﹠Chemicals Inc. manufacturing), FloradFC430, FC431 (trade name, Sumitom 3 M K.K. manufacturing), Asahi Guard AG10, SurflonS382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068 (trade name, Asahi Glass company limited makes); Anionic surfactant is as W004, W005, W017 (trade name, YushoK.K. makes); Polymeric dispersant is as EFKA-46, EFKA-47, EFKA-450 (trade name, MorishitaSangyo K.K. makes), dispersing aid 6, dispersing aid 8, dispersing aid 15, dispersing aid 9100 (trade name, Sun Nopko makes) or the like; Various spreading agents are as Solsperse 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (trade name, Geneka K.K. makes); AdekaPluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, F84, P94, L101, P103, F108, L121, P-123 (trade name, Asahi Denka Kogyo K.K. makes) and IsonetS-20 (trade name, Sanyo chemical industry company limited makes).

Next, the embodiment of the preferred use of the pigment dispersion that so obtains is described.

The average grain granularity (particle mean size) of pigment is very important.When particle mean size is big, the light scattering that generation is not expected, the result is when as photosensitive material, and its penetrability reduces, and the necessary light of photopolymerization can not be provided in the photographic layer.When the light that uses shorter wavelength during as light source scattering more obvious.Therefore, use in the sensitive offset press version presoma of relative shorter wavelength light source the objective of the invention is, the particle mean size of preferred pigments is as much as possible little.The penetrability that scattering the caused decline of depending on grain graininess as mentioned above is tangible.Even selects the structure of pigment dyeing thing and set absorptive character aptly, but when grain graininess was big, the penetrability under the 400nm still reduced, and caused that the light sensitivity internal ground of photographic layer descends so that the penetrability under the 400nm is increased.On the other hand, when grain graininess is too little, it is not enough that dispersion stabilization is tending towards, and also occur in the photographic layer not expecting problem such as coalescent, precipitation or the like.By these viewpoints, the average grain granularity of the used pigment of expectation the present invention is 0.01-0.7 μ m, more expects 0.01-0.4 μ m.Say that more specifically the preferred particulates granularity is that 0.4 μ m or lower proportion of particles account for the 70wt% of total particle quantity or more, more preferably 80wt%, and average grain granularity is 0.01-0.4 μ m, more preferably 0.02-0.35 μ m.

The upper limit of used amount of pigment among control the present invention is so that the development processing characteristics of the polymerization activity of not obvious reduction photographic layer component and sensitive offset press version presoma.On the other hand, its lower limit set is for obtaining to improve enough effects of photographic fog.These differences depend on the optical property of each pigment.0.01-5g/m normally ², preferred 0.05-4g/m ², more preferably 0.1-2g/m ²On the other hand, judge that because pigment has superior photographic fog performance in the photographic layer, so the absorbance under the 500nm is 0.1 or higher, preferred 0.3 or higher, more preferably 0.5 or higher by optical property.

In addition, the known method of various routines also is fit to the required use of pigment.Specifically, if coexistence has the polymkeric substance that has aliphatic double bond on its main chain or the side chain in dispersed color,, can obtain photographic layer than ISO as describing among the JP-A 8-101498.In addition, in optical polymer system, use the routine of pigment to propose visible JP-A 10-282647 and 9-230601 or the like.Other component

In the photographic layer of lithographic plate presoma, can use extremely production method etc. of other component of be fit to using aptly.Sensitizing pigment

In the photographic layer of lithographic plate presoma of the present invention, can use sensitizing pigment aptly if desired, be used to strengthen light sensitivity.This sensitizing pigment is used with above-mentioned cyclopentadiene titanium compound and so-called optical initiator system.Preferred sensitizing pigment has photo absorption performance in photographic layer, its absorbance under 400nm is higher than the absorbance under the 500nm.Other preferred sensitizing pigment has optics light sensitivity performance, and wherein maximum wavelength photoreceptor is more preferably less than 430nm less than 450nm, and is longer than 300nm, more preferably is longer than 350nm.Can not limit the use of sensitizing pigment among the present invention, as long as it satisfies these characteristics.

As sensitizing pigment with these performances, for example by part cyanine pigment shown in the following general formula formula (1), by the styryl pigment shown in the following general formula (2), by the benzopyrene shown in the following general formula (3), cumarin, by the aromatic ketone shown in the following general formula (4), by anthracene shown in the following general formula (5) or the like. Wherein A represents S atom or NR ₁, R ₁Expression monovalence non-metal atom group; Y represents contiguous A and non-metal atom group, and its carbon atom with vicinity forms the basic nuclear of pigment; X ₁And X ₂The monovalence non-metal atom group is represented in expression independently separately, and X ₁And X ₂Can mutually combine, form the acid core of pigment.

X wherein ₁And X ₂Such as general formula (1) definition; R ₂To R ₆Represent the monovalence non-metal atom group independently of one another, and preferred at least one R ₂To R ₆It is the electron substituent group of giving with negative Hammett ' s substituent constant.

General formula (3) partial structural formula (1)

Wherein Y represents carbonyl, thiocarbonyl, imino group or the alkylidene of being represented by above-mentioned partial structural formula (1); X ₁And X ₂Define as general formula (1); And R ₇To R ₁₂Represent the monovalence non-metal atom group independently of one another.

(inserting original text P72 general formula 4)

Ar wherein ₁Expression aromatic group or heteroaromatic group optionally have substituting group on it; R ₁₃Represent the monovalence non-metal atom group independently.Preferred R ₁₃Expression aromatic group or heteroaromatic combination, and Ar ₁And R ₁₃Can interosculate and form ring. X wherein ₂, X ₄, R ₁₄To R ₁₂Represent the monovalence non-metal atom group independently of one another.Preferred X ₃And X ₄Expression has the electron substituent group of giving of negative Hammett ' s substituent constant.

At general formula (1) in (5), X ₁To X ₄And R ₁To R ₁₂The preferred embodiment of the monovalence non-metal atom group of expression comprises hydrogen atom; Alkyl is (as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, the s-butyl, the tert-butyl group, isopentyl, neopentyl, the 1-methyl butyl, isohesyl, the 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, the 2-norborny, chloromethyl, bromomethyl, the 2-chloroethyl, trifluoromethyl, methoxy, methoxy ethoxy, the allyloxy methyl, phenoxymethyl, methyl mercapto, toluene sulfenyl methyl, the ethylamino ethyl, the diethylamino propyl group, morpholinyl propyl, acetoxy-methyl, the benzoyloxy methyl, N-cyclohexyl carboxyamide base oxygen base ethyl, N-phenyl amino formoxyl oxygen base ethyl, the acetyl-amino ethyl, N-methyl benzoyl aminopropyl, the 2-oxoethyl, the 2-oxopropyl, the carbonyl propyl group, the methoxycarbonyl ethyl, the allyloxy carbonyl butyl, chlorophenoxy carbonyl methyl, the carbamyl ylmethyl, N-methylamino formoxyl ethyl, N, N-dipropyl carbamyl, N-(methoxyphenyl) carbamyl, N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl, the sulfo group butyl, sulfonate radical closes butyl, the sulfonamide butyl, N-ethyl sulfonamide methyl, N, N-dipropyl sulfonamide propyl group, N-tolyl sulfonamide propyl group, N-methyl-N-(phosphono phenyl) sulfonamide octyl group), the phosphono butyl, phosphonate radical closes hexyl, the diethyl phosphonyl butyl, diphenylphosphine acyl group propyl group, methylphosphine acyl group butyl, the methylphosphine acid group closes butyl, tolylphosphine acyl group hexyl, the tolylphosphine acid group closes hexyl, phosphono oxygen base propyl group, phosphonate radical closes oxygen Ji Dingji, benzyl, ethoxyphenyl, the α methyl-benzyl, 1-methyl isophthalic acid-phenylethyl, to methyl-benzyl, cinnamyl, allyl, 1-propenyl methyl, the 2-butenyl group, the 2-methacrylic, 2-metering system ylmethyl, 2-propynyl, the 2-butynyl, the 3-butynyl); Aryl is (as phenyl, diphenyl, naphthyl, tolyl, xylyl, trimethylphenyl, cumyl, chlorphenyl, bromophenyl, chloromethyl phenyl, hydroxy phenyl, methoxyphenyl, ethoxyl phenenyl, Phenoxyphenyl, the acetoxyl group phenyl, the benzoyl phenyl, the methylbenzene sulfenyl, the phenyl thiophenyl, the methylamino phenyl, dimethylaminophenyl, the acetyl-amino phenyl, carboxyl phenyl, methoxy carbonic acid phenyl, the ethoxyl phenenyl carbonyl, the carbobenzoxy phenyl, N-phenyl amino formoxyl phenyl, phenyl, cyano-phenyl, the sulfo group phenyl, the sulfonic group phenyl, the phosphono phenyl, phosphonate radical closes phenyl or the like); Heteroaryl is (as thiophene, thiophene Xanthones (thiathrene), furans, pyrans, isobenzofuran, cumene (curomene), xanthene, phenoxazine, pyrroles, pyrazoles, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indoline, isoindoline, indyl, indazole, purine, quinoline, isoquinoline, phthalazines, naphthyridines, phenanthrene, acridine, piperidines (perymidine), phenanthroline, phthalazines, nardil (phenalzasine), phenoxazine, furazan, phenoxazine or the like); Alkenyl (as vinyl, 1-propenyl, 1-butenyl group, cinnamyl, 2-chloro-1-vinyl or the like); Alkenyl (for example ethinyl, 1-propinyl, 1-butynyl, trimethyl silyl ethinyl or the like); Halogen atom (Fr;-Br.-Cl;-I); hydroxyl; alkoxy; aryloxy group; sulfydryl; the sulfane base; the sulphur aryl; the disulphanes base; two sulphur aryl; amino; the N-alkyl amino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamyl oxygen base; N-alkyl-carbamoyl oxygen base; N-aryl-amino-carbonyl oxygen base; N; N-dialkyl amido formoxyl; N; the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; alkyl sulfide oxygen base; aryl sulphur oxygen base; sulfonyl; acyl amino; N-alkyl acyl amino; N-aryl-acyl amino; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N ' N '-dialkyl group-N-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N; ' N '-diaryl-N-alkyl urea groups; N '; N '-diaryl-N-aryl-ureido; N '-alkyl N-aryl-N-alkyl urea groups; N '-alkyl-N-aryl-N-aryl-ureido; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxy carbonylamino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxy carbonylamino; formoxyl; acetyl group; carboxyl; alkoxy carbonyl; the aryloxy carbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; N-aryl-amino-carbonyl oxygen base; N, the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; the alkyl sulfinyl; the aryl sulfinyl; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO ₃H) and conjugation basic group (after this be called sulfonate radical and close group); the alkoxy sulfonyl; aryl and sulfonyl; amino sulfinyl (sulfinamoyl); N-alkyl amino sulfinyl (sulfinamoyl); N; N-dialkyl amido sulfinyl (sulfinamoyl); N-arylamino sulfinyl (sulfinamoyl); N; N-ammonia diaryl base sulfinyl (sulfinamoyl); N-alkyl-N-arylamino sulfinyl (sulfinamoyl); sulfamoyl; the N-alkylsulfamoyl group; N; the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N, N-ammonia diaryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; phosphono (PO ₃H ₂) and conjugation basic group (after this be called sulfonate radical and close group), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(aryl) ₂), an alkylphosphines acyl group (PO ₃(alkyl)) and conjugation basic group (after this be called alkyl woods acid group and close group), an aryl phosphine acyl group (PO ₃(aryl)) and conjugation basic group (after this be called aryl woods acid group and close group), phosphonato (OPO ₃H ₂) and conjugation basic group (after this be called sulfonate radical and close the oxygen base), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), an alkylphosphines acyloxy (OPO ₃(alkyl)) and conjugation basic group (after this be called alkyl woods acid group and close the oxygen base), an aryl phosphine acyloxy (OPO ₃(aryl)) and conjugation basic group (after this be called aryl woods acid group and close the oxygen base), cyano group, nitro or the like, in the above-mentioned substituting group, preferred especially hydrogen atom, alkyl, aryl, halogen atom, alkoxy and acyl group.

In general formula (1), link to each other with the Y taproot of the pigment that forms and continuous carbon atom of A has and contains 5,6, and the heterocycle of 7-unit's nitrogen-atoms or sulfur atom-containing is preferred 5,6-unit heterocycle.

The heterocycle of nitrogen atom can use for example people " U.S. chemical institute magazine " 73 such as L.G.Brooker, those of any part of cyanine pigment described in 5326-5358 (1951) and the reference and known formation taproot aptly.Its example comprises thiazoles (thiazole for example, the 4-methylthiazol, the 4-phenyl thiazole, the 5-methylthiazol, the 5-phenyl thiazole, 4, the 5-dimethylthiazole, 4,5-diphenyl thiazole, 4,5-two (p-methoxyphenyl thiazole), 4-(2-thienyl) thiazole etc.), benzothiazoles (benzothiazole for example, the 4-chloro benzothiazole, the 5-chloro benzothiazole, the 6-chloro benzothiazole, the 7-chloro benzothiazole, the 4-methylbenzothiazole, the 5-methylbenzothiazole, the 6-methylbenzothiazole, the 5-bromo benzothiazole, 4-phenyl benzothiazole, 5-phenyl benzothiazole, 4-methoxyl benzo thiazole, 5-methoxyl benzo thiazole, 6-methoxyl benzo thiazole, 5-iodobenzene and thiazole, 6-iodobenzene and thiazole, the 4-ethoxyl benzo thiazole, the 5-ethoxyl benzo thiazole, the tetrahydro benzo thiazole, 5,6-dimethoxy benzo thiazole, 5,6-dioxy vinyl benzo thiazole, the 5-hydroxybenzothiazole, the 6-hydroxybenzothiazole, 6-dimethylamino benzo thiazole, 5-carbethoxyl group benzothiazole etc.), (for example naphthalene [1 for the naphthothiazoles class, 2] thiazole, naphthalene [2,1] thiazole, 5-methoxynaphthalene [2,1] thiazole, 5-ethoxy naphthalene [2,1] thiazole, 8-methoxynaphthalene [1,2] thiazole, 7-methoxynaphthalene [1,2] thiazole etc.), benzo-thiophene-7 ', 6 ', 4, the 5-thiazoles (for example 4 '-methoxyl benzo-thiophene-7 ', 6 ', 4,5-thiazole etc.) oxazole class (4-Jia Ji oxazole for example, 5-Jia Ji oxazole, 4-Ben Ji oxazole, 4, the 5-diphenyl-oxazole, 4-Yi Ji oxazole, 4,5-Er Jia Ji oxazole, 5-Ben Ji oxazole etc.) Benzooxazole kind (benzoxazole, 5-Lv benzoxazole, 5-Jia base benzoxazole, 5-Jia base benzoxazole, 5-Ben base benzoxazole, 6-Jia base benzoxazole, 5, the 6-benzoxazole dimethyl, 4, the 6-benzoxazole dimethyl, 6-methoxyl benzo oxazole, 5-methoxyl benzo oxazole, 6-methoxyl benzo oxazole, 4-ethoxy benzo oxazole, 5-Lv benzoxazole, 6-methoxyl benzo oxazole, 5-Qiang base benzoxazole, 6-Qiang base benzoxazoles etc.) (for example naphthalene [1 for naphthoxazole class, 2] oxazoles, naphthalene [2,1] oxazole etc.), selenazoles class (4-methyl selenazoles for example, 4-phenyl selenazoles etc.), benzo selenazoles class (benzo selenazoles for example, 5-chlorobenzene and selenazoles, 5-methoxyl benzo selenazoles, 5-hydroxy benzo selenazoles, tetrahydro benzo selenazoles etc.), (for example naphthalene [1 for naphthalene selenazoles class, 2] selenazoles, naphthalene [2,1] selenazoles etc.), Thiazoling type (thiazoline for example, 4-methylthiazol quinoline etc.), 2-quinolines (quinoline for example, the 3-methylquinoline, the 5-methylquinoline, the 7-methylquinoline, the 8-methylquinoline, the 6-chloroquinoline, the 8-chloroquinoline, the 6-methoxy quinoline, the 6-methoxy quinoline, the 6-hydroxyquinoline, oxine etc.), 4-quinolines (quinoline for example, the 6-methoxy quinoline, the 7-methylquinoline, 8-methylquinoline etc.), 1-iloquinoline derivative (isoquinoline for example, 3,4-dihydro-isoquinoline etc.), 3-iloquinoline derivative (for example isoquinoline etc.), benzimidazole (for example 1,3-diethyl benzo imidazoles, 1-ethyl-3-phenyl benzimidazole etc.), 3,3-dialkyl group indolenine class (for example 3,3-diethyl indolenine, 3,3, the 5-tri-methyl indole false, 3,3,7-tri-methyl indole false etc.), 2-pyridines (pyridine for example, 5-picoline etc.), 4-pyridines (for example pyridine etc.); Or the like.

The example of sulfur heterocyclic ring for example has the dithiol part-structure in the pigment described in the flat 3-296759A of JP-.

Its object lesson comprises benzothiazoles (for example benzothiazole, 5-tert-butyl group benzo thiazole, 5-methylbenzothiazole etc.), (for example naphthalene [1 for the naphthyl disulfide phenols, 2] dithiol, naphthalene [2,1] dithiol etc.), the dithiol class (for example 4,5-DMDS phenols, 4-phenyl dithiol class, 4-methoxycarbonyl dithiol class, 4,5-dimethoxy carbonyl benzo dithiol class, 4,5-two trifluoromethyls two mercaptan, 4,5-dicyano two mercaptan, 4-methoxycarbonyl methyl two mercaptan, 4-ethyloic two mercaptan etc.), or the like.

Although when the above-mentioned heterocycle of explanation, use the female skeleton title of heterocycle for convenience's sake always, but the time as the basic framework part-structure of sensitizing pigment, benzothiazole skeleton for example, replacement form with the alkylidene type adds, its degree of unsaturation reduces by 1 degree, as-2 (3H) benzothiazole subunit of 3-replacement.

The more specifically example of sensitizing pigment is shown in down with general formula (1)-(5).Yet, can be used for sensitizing pigment of the present invention and be not limited to these.

In order to improve the performance of photographic layer, can carry out various chemical modifications to sensitizing pigment of the present invention.For example; can obviously increase the exposure film strength; and by covalent bond, ionic link, hydrogen bond etc. but sensitizing pigment is attached on the above-mentioned addition polymerization compound structure (for example acryloyl group, methacryl) unnecessary the separating of can suppress to expose back pigment and this film.And, by with sensitizing pigment and above-mentioned cyclopentadiene titanium compound and other free-radical generating part (for example, the position of reducible decomposition such as alkyl halide,, superoxide, two imidazoles,, two imidazoles etc.; Oxygenolysis position such as borate, amine, trimethyl silyl methyl, ethyloic, carbonyl, imines etc.) combination, can obviously improve photonasty under the light-initiated system of special low concentration.And, in order to improve the suitability of in being preferred for (alkalescence) moisture developing solution of photographic layer, handling, should add hydrophilic site (acidic group or polar group such as carboxyl and ester thereof, sulfo group and ester thereof, ethylene oxide group etc.) effectively.Especially, because the relative hydrophobic structure of ester class hydrophilic radical and its produce acidic group by hydrolysis and increased water wettability in developer solution, so it has the feature of excellent compatibility in photographic layer.In addition, in order to improve the compatibility in photographic layer and to suppress crystallization deposition, for example can add substituting group aptly.For example, in certain photosensitive system, for example the unsaturated link of aromatic radical, allyl etc. can improve compatibility by the utmost point effectively, and adds steric hindrance between the pigment π plane according to the method that for example adds branched-alkyl structure etc., can suppress crystallization deposition significantly.And, epoxy radicals phosphate-based by adding, trialkoxysilyl etc. can improve metal, metal oxide etc. and contact with the tight of inorganics.In addition, also can use method of for example preparing the sensitizing pigment polymer or the like according to purpose.

According to the hope performance of photosensitive material, the suitably structure kind of the details of method of adjustment such as these sensitizing pigment, single use or use two or more jointly and addition.For example, use two or more sensitizing pigment together, can improve the compatibility of the photographic layer of sensitive offset press version presoma of the present invention.Aspect selection sensitizing pigment, except photonasty, the molar absorption coefficient under the emission wavelength of used light source also is an important factor.Because addition can reduce relatively when using the big pigment of molar absorption coefficient, is economical therefore, also be useful to the film character of photographic layer.Because the photonasty and the resolution of the photographic layer of sensitive offset press version presoma of the present invention, and be subjected to absorbance under the optical source wavelength to influence the physical property of big exposed film, therefore select the addition of sensitizing pigment aptly according to these elements.For example, absorbance be low to moderate 0.1 or lower regional photonasty reduce.And, reduce resolution by the halation influence.Yet, in order to make 5 microns or thicker film sclerosis, the more suitable sometimes increase hardenability of this low absorbance.Be higher than 3 zone in absorbance, most of light are absorbed in the surface of photographic layer, be suppressed in sclerosis than further portion, for example, and when when the galley, film strength and contact not enough with substrate tight.When using less relatively thickness, the addition of the preferred sensitizing of control like this pigment: its photographic layer absorbance is 0.1-1.5, preferred 0.25-1.Weight in the photographic layer component is 100 parts, often is the 0.05-30 weight portion, preferred 0.1-20 weight portion, more preferably 0.2-10 weight portion.Binder polymer

The preferred binder polymer that uses in the photographic layer of sensitive offset press version presoma of the present invention.As bonding agent, preferably contain the bigger linear organic polymer of molecular weight.As this molecular weight bigger " linear organic polymer ", can use any one.Preferably have the dissolubility of water-soluble or weak base aqueous solution or expansiveness, can water development or the bigger linear organic polymer of molecular weight that develops of weak base aqueous solution.Not only according to purposes, and according to purposes, select and use the bigger linear organic polymer of molecular weight as water, weak base aqueous solution or organic solvent developer as the film forming agent of photographic layer.For example, when using the bigger water-soluble organic polymer of molecular weight, make it can water development.As the bigger linear organic polymer of this molecular weight, the addition polymer that has a carboxyl on side chain is arranged, for example, at described in the clear 59-44615A of JP-, the clear 54-34327B of JP-, 58-12577,54-25957, the clear 54-92723A of JP-, 59-53836 and the 59-71048 those, that is, economic acrylic copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc.Similarly, have the acid cellulose of carboxyl derivant is arranged on side chain.In addition, also can use by cyclic acid anhydride being added to those that obtain in the addition polymer with hydroxyl.

Especially, wherein, because [(methyl) benzyl acrylate/(methyl) but the vinyl monomer of acrylic acid/other addition polymerization if necessary] multipolymer and [(methyl) allyl acrylate/(methyl) but the vinyl monomer of acrylic acid/other addition polymerization if necessary] multipolymer be balance film intensity, photonasty and development character well, so they suit.

Have good especially intensity at polyurethane binder polymkeric substance that contains acidic group described in the flat 7-12004B of JP-, 7-120041,7-120042 and the clear 63-287944A of 8-12424, JP-, 63-287947 and 1-271741 and the Japanese patent application 10-116232, thereby have good ability that stands duplicate printing and lower exposure suitability.

Owing to have good developing performance and good film strength simultaneously at the bonding agent described in the flat 11-171907A of JP-, so they suit also with acylamino-.

And, as the water-soluble linear organic polymer, also can use polyvinylpyrrolidone, polyoxyethylene etc.In order to improve the oxidation film strength, also can use the polyethers of producing by alcohol soluble nylon or 2,2-two-(4-hydroxyphenyl) propane and chloropropylene oxide etc.In all photographic layer components, can any amount mix the bigger linear organic polymer of these molecular weight.Yet, when it surpasses 90wt%, can not obtain best result from the viewpoints such as intensity that form image.Preferred 30-85wt%.Weight ratio with the bigger linear organic polymer of the compound of photopolymerization vinyl unsaturated double-bond and molecular weight is preferably 1/9-7/3.In a preferred embodiment, use water-soluble hardly and be dissolved in alkali binder polymer.Thus, organic solvent can be ignored the unfavorable of environment, perhaps is restricted to minimum use amount in developing solution.In the method, from image intensity and suitable acid number (is acid content/g polymkeric substance according to chemical equivalent) and the molecular weight of selecting binder polymer of developing performance.The preferred 0.4-3.0meq/g of this acid number, the preferred 3000-500000 of molecular weight, more preferably, acid number is 0.6-2.0, molecular weight is 10000-300000.Auxiliary sensitizer

Can obtain higher photonasty by the photographic layer that uses certain adjuvant (below be referred to as auxiliary sensitizer) sensitive offset press version presoma of the present invention.Its mechanism of action is not clear, it is believed that it is following chemical process in many cases.That is, suppose a living radical be in light reaction procedure that the above-mentioned light-initiated system by light absorption causes and following polyaddition reaction, take place by auxiliary sensitizer and the new generation of various intermediate activity kind (free radical, superoxide, oxygenant, reductive agent etc.) reaction.Be divided into (a) reduction roughly to produce those of living radical, (b) oxidation with produce living radical those and (c) be converted into those of the high free radical of activity with active low free radical reaction, and every kind of compound often lacks Latin.(a) reduction is to produce the compound of free radical

Compound with carbon-halogen bond: it is believed that the fracture of carbon-halogen bond reductibility produces living radical.Especially, for example can use trihalomethyl-2-three azines, three halogen methoxyl azines etc. aptly.

Compound with nitrogen-nitrogen key: it is believed that nitrogen-nitrogen base reductibility fracture produces living radical.Especially, for example, use Hexaarylbisimidazolecompounds etc. aptly.

Compound with o-o bond: it is believed that the fracture of o-o bond reductibility ground produces living radical.Especially, for example, use organic peroxide etc. aptly.

Compound: it is believed that also original place fracture generation living radical of carbon-heterodesmic and oxygen-nitrogen key.Especially, for example diaryl group iodized salt, triaryl sulfonium salts, N-alkoxy pyridines (azine) salt etc. of suitable use.

Pherocene, iron propadiene complex compound: can reduce real estate liveliness proof free radical.(b) oxidation is to produce the compound of living radical

Arrcostab complex compound: it is believed that carbon-heterodesmic oxidation ground fracture produces living radical.Especially, suitable use boric acid triaryl Arrcostab for example.

Alkyl ammonium compounds: it is believed that the C-X key that carbon links to each other with nitrogen produces living radical through oxidation scission.As X, hydrogen atom is arranged, carboxyl, trimethyl silyl, benzyl etc. can suit.Especially, ethanolamines, N-phenylglycine class, N-trimethyl silyl dimethoxym ethane imines etc. are for example arranged.

Sulfur-bearing, sn-containing compound: those that obtain by the nitrogen-atoms of replacing with sulphur atom and tin atom in the above-mentioned amine can produce living radical by same function.Also known compound with S-S key confirms the sensitizing by fracture S-S.

The methyl carbonyls of alpha-substituted: can produce living radical by oxidation scission carbonyl-α-carbon bond.And, demonstrate same function by those that carbonyl are changed into oxime ether obtains.Especially, 2-alkyl-1-[4-(alkylthio) phenyl is arranged]-2-morpholine pronone-1 class, and, then N-OH is converted to the oxime ether that ether obtains by with pronone class and the reaction of azanol class.

Sulfinate: can reduce the generation living radical.Especially, aryl sulfinic acid sodium etc. is arranged.

(c) give high mars free radical with free radical reaction, or the compound of using as chain-transferring agent: for example, use compound and molecule thereof with SH, PH, SiH, GeH.These materials are given hydrogen to SA free radical kind, thereby produce free radical, perhaps can be oxidized, then,, thereby produce free radical through deprotonation.Especially, 2-mercaptobenzimidazole etc. is for example arranged.

As the example more specifically of these auxiliary sensitizers, for example in the flat 9-236913A of JP-, chemical compound lot has been described, with it as being intended to improve photosensitive adjuvant.These compound middle parts are respectively in down.But the present invention is not limited to this.

About these auxiliary sensitizers, for the performance of the photographic layer that improves sensitive offset press version presoma of the present invention, can also be identical with above-mentioned sensitizing pigment, carry out various chemical modifications.For example, combine but can utilize, add hydrophilic site, add the substituting group that is used to improve compatibility and suppresses crystallization deposition with unsaturated compound and other part of sensitizing pigment, activating agent addition polymerization, add the substituting group that improves closely contact, polymkeric substance formation, or the like.

These sensitizers can use separately, also can two or more be used in combination.Weight in compound with vinylation unsaturated double-bond is 100 parts, and use amount is suitably the 0.05-100 weight portion, is preferably the 1-80 weight portion, more preferably the 3-50 weight portion.Polymerization initiator

And, in the present invention, add ideally to be used on a small quantity be suppressed at and produce respectively or unnecessary thermal polymerization has the compound of polymerizable vinyl unsaturated double-bond during storage photographic layer components composition thermal polymerization prevents agent.Prevent agent as suitable thermal polymerization, quinhydrones, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzoquinones, 4 are arranged, 4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), N-nitrosophenyl hydroxylamine cerium (I) salt etc.In composition total weight, thermal polymerization prevents that the addition of agent is preferably the about 5wt% of about 0.01wt%-.If necessary, can also add advanced higher fatty acid derivative such as docosanoic acid and docosane acid amides, and after the photographic layer of coating sensitive offset press version presoma of the present invention, in dry run, make on its surface existence unevenly, cause through the oxygen polymerization preventing at photographic layer.In the weight of whole composition, the addition of advanced higher fatty acid derivative is preferably the about 10wt% of about 0.5wt%-.Colorant

And, painted for the photographic layer that makes sensitive offset press version presoma of the present invention, can add colorant as dyestuff or pigment.By adding colorant, can improve the suitability that so-called lithographic plate is checked visuality after performance such as lithographic plate are produced, measured machine as the image color of galley.As colorant, because most of dyestuffs cause the photonasty of photo-polymerization type photographic layer to reduce, therefore special preferred pigments.As its object lesson, phthalocyanine color, AZO pigments, the pigment as carbon black, titanium oxide etc., ethyl violet, crystal violet, azo dyes, anthraquinone dye, cyanine dye etc. are for example arranged.In the weight of whole composition, the addition of dyestuff and pigment is preferably the about 5wt% of about 0.5wt%-.Other adjuvant

And the physical property for the cured film of the photographic layer that improves sensitive offset press version of the present invention can also add known additives, as inorganic filler, other plastifier, can improve printing ink at sensitizer of the lip-deep adhesion property of photographic layer etc.

The example of plastifier comprises dioctyl phthalate, phthalic acid docosyl ester, triethylene glycol dicaprylate, phthalic acid diethyl diester, phosphonic acids front three phenyl ester, dioctyl adipate, dibutyl sebacate, glycerol triacetate etc.When using bonding agent,, can add 10wt% or amount still less in the compound with vinyl unsaturated double-bond and the total amount of this bonding agent.

And, can also add UV initiating agent, thermal cross-linking agent etc., to strengthen the effect of developing the back heating and exposing for the film strength (standing the ability of duplicate printing) that improves the described sensitive offset press version presoma of the present invention in back.

In addition, contact with the tight of substrate of sensitive offset press version presoma of the present invention, and the development that improves unexposed photographic layer removes ability, can use adjuvant and the middle layer can be provided in order to improve photographic layer.For example, have relative strong interactional compound with substrate, for example have the compound, phosphine thing of diazonium structure etc., can improve tight contact and can improve the ability that stands duplicate printing by adding or coating.By adding or being coated with hydrophilic polymer such as polyacrylic acid and poly-sulfonic acid, can improve the development character and the dyeing patience of non-image part as primer.

When being coated with the photographic layer of sensitive offset press version presoma of the present invention on the described in the back substrate, be dissolved in the various organic solvents described photographic layer component and use.The example of solvent for use comprises acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, the glycol monomethyl isopropyl ether, ethylene glycol monomethyl ether acetate, the 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl propyl ester, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, methyl lactate, ethyl lactate etc.These solvents can be used alone or in combination.The suitable concentration of solid constituent in coating fluid is 2-50wt%.

Because coating weight is influential with the ability that stands duplicate printing to the photonasty and the developing performance of photographic layer and the film strength of exposing, ideally according to the suitable coating weight of selecting on-chip photographic layer of its purposes.When coating weight very little the time, print the patience deficiency.On the other hand, measure when too many, photonasty reduces, and exposure needs the longer time, and in addition, development treatment also undesirably needs the longer time.In sensitive offset press version presoma of the present invention, in dried weight, coating weight is suitably about 0.1g/m ²-Yue 10g/m ²More preferably 0.5-5g/m ²Protective seam

In sensitive offset press version presoma of the present invention,, therefore preferably also on photographic layer, provide a protective seam owing in the atmosphere of being everlasting, expose.This protective seam has prevented to be present in the atmosphere and has stoped to expose in the photographic layer and caused that image forms low compound such as oxygen, the alkaline matter etc. of molecular weight that react and sneaks in the photographic layer, and can expose in atmosphere.Therefore; the required performance of this protective seam is the hyposmosis ability of low compound of molecular weight such as oxygen etc., and, this protective seam light conduction of suppressing hardly to be used to expose ideally; and have good tight contact with photographic layer, and can in developing process, easily remove after the exposure.

Design aforesaid protective seam routinely, and be described in detail among US3458311 and the clear 55-49729A of JP-.

About can be used for the material in the protective seam; use water-soluble polymers valuably with suitable excellent crystallinity; particularly known water-soluble polymers for example has polyvinyl alcohol (PVA), polyvinylpyrrolidone, acid cellulose, gelatin, Arabic gum, polyacrylic acid etc.; wherein;, obtain as key component as pectin/polyvinyl alcohol as the best result who removes the key property of performance as oxygen isolation performance and development.The polyvinyl alcohol (PVA) that is used for protective seam can also partly use ester, ether and acetal to replace, and is useful on essential oxygen isolation performance of acquisition and water miscible unsubstituted vinyl alcohol as long as it contains.Similarly, can also partly contain other copolymerization component.As the object lesson of polyvinyl alcohol (PVA), 71-100% is arranged, and hydrolysis and molecular weight are those of 300-2400.Object lesson comprises that (these all are trade names for PVA-105, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, L-8 etc.; By Kuraray Co., Ltd. produces)

According to photographic fog, the closely component (selection of PVA, the use of adjuvant), its coating weight etc. of contact and scratch patience and oxygen isolation and removing property of development selection protective seam.In general, when the hydrolysis of used PVA was bigger than high (when the content of substituted ethylene alcohol unit in protective seam is not higher) and film thickness, the oxygen isolation performance further increased, and can obtain advantage from the photonasty angle.But, when the oxygen isolation performance improves when excessive, can cause produce and storage in unnecessary polyreaction takes place and unnecessary photographic fog takes place during at image exposure and produce problems such as thick image line.To contact and abrade patience also of crucial importance to operation with image section tight.That is, if when the hydrophilic layer of being made by water-soluble polymers is laminated on the oleophylic polymer layer, because bonding deficiency easily takes place, so film peels off, and released part suppresses and causes the defective of film sclerosis difference for example etc. through the polymerization of oxygen.In order to address this problem, various suggestions have been proposed to improve this bonding between two-layer.For example, US292501 and 44563 has described acrylic emulsion or water-insoluble vinylpyrrolidone/vinyl acetate copolymer or analog has been mixed in the hydrophilic polymer of mainly being made up of polyvinyl alcohol (PVA) with the amount of 20-60wt%, and this mixture layer is pressed on the binding layer, thereby obtains enough bonding.Can use arbitrarily these known technologies are coated with protective seam in sensitive offset press version presoma of the present invention.The method that is coated with this protective seam for example is described in detail among the US348311 and the clear 55-49729A of JP-.

And, can also give other function to protective seam.For example, the performance of the light transmission by add confirming to have good 350nm-450nm and can absorb the colorant (water-soluble dye etc.) of the light more than the 500nm effectively can further improve the safety light performance under the situation that photonasty is reduced.

Sensitive offset press version presoma of the present invention often accurately exposes through image, and then, the unexposed portion of photographic layer is removed by developer solution, thereby obtains image.As producing used preferred developer solution in the lithographic plate by this sensitive offset press version presoma, developer solution described in the clear 57-7427B of JP-is arranged, and as the inorganic alkaline agents aqueous solution of sodium silicate, potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, uncle's Alendronate, secondary Alendronate, tertiary phosphine acid ammonium, secondary phosphine acid ammonium, sodium metasilicate, sodium bicarbonate, ammoniacal liquor etc. and as monoethanolamine, diethanolamine etc. organic basic reagent water solution suit.Add these alkaline solutions, its concentration is 0.1-10wt%, preferred 0.5-5wt%.

If necessary, these alkaline aqueous solutions can contain a spot of surfactant, and organic solvent such as phenmethylol, 2-phenoxetol and butoxy ethanol.For example, described in US3375171 and 3615480 those are arranged.And, also very good at the developer solution described in the clear 50-26601A of JP-, the clear 56-39464B of 58-54341, JP-and the 56-42860.

In addition, as the method for producing lithographic plate by sensitive offset press version presoma of the present invention, if necessary, can be before exposure, in the exposure process or exposure and develop between whole surface is heated.Be heated by this, promote that the image in photographic layer forms reaction, also have as improving photonasty and standing advantages such as ability, the photonasty of duplicate printing is stable.And, in order to improve image intensity and the ability that stands duplicate printing, also can carry out aftertreatment effectively and the exposure on the entire image surface, back of developing.Preferred at 150 ℃ or more heat-treat under the weaker condition of low temperature before developing through being everlasting.When temperature is too high, the problem of photographic fog to non-image part can take place, or the like.After developing, utilize extremely exacting terms to heat-treat.Often, be at 200-500 ℃.When temperature is too low, can not obtain enough image intensification effects, when too high, can produce problem as substrate destruction, image section thermal decomposition etc.

As expose with digital image information and the system of the CTP that develops in, promptly main system is subjected to the conflict of sensitive offset press version presoma of the present invention, can use good especially development treatment method.In this system, obtain digital image information in advance.Can develop with the best of this information comparison then and treatment conditions are transferred on the opertaing device of lithographic plate treatment facility of automatic processing machine for example etc.Can when selecting optimum development and treatment conditions (developer solution magnitude of recruitment, development temperature, development time, aftertreatment time etc.) aptly, handle then.By this step, can improve Treatment Stability significantly, and print capacity can be kept constant.For example, the flat 11-15144A of JP-has proposed a kind of method, wherein there are not the area information A (m2) of image section and the control section that lithographic plate information X is stored in automatic processing machine, replenish aptly according to corresponding to these information with undefined magnitude of recruitment, and when the use amount with developer solution is controlled at minimum level, increase fast the treatment capacity of plate.

Automatically area magnitude of recruitment (the ml)=area of developer solution replenishes than Rx (ml/m ²) * area A (m ²)

Here, the Rx representative is as version X 1m ²Required magnitude of recruitment (ml) during the whole surface development of non-image part.

When sensitive offset press version presoma of the present invention exposes, can use known method without restriction.The desired wavelength of light source is 350nm-450nm, and especially, the InGaN semiconductor laser suits.As exposure mechanism, inside surface rotating-cylinder method, outside surface rotating-cylinder method, lithographic plate method etc. all can be accepted, by using water-soluble high those, the photographic layer component of sensitive offset press version presoma of the present invention can be dissolved in neutral water and the alkalescent water, simultaneously, also the lithographic plate presoma with this structure can be installed on the printer exposure and development on this machine then.

As available 350nm-450nm lasing light emitter, can utilize following source.

Gas laser, for example Ar ion laser (364nm, 351nm, 10mW-1W), Kr ion laser (356nm, 351nm, 10mW-1W) and He-Cd laser (441nm, 325nm, 1mW-100mW).

Solid State Laser, for example Nd:YAG (YVO ₄) and the combination (355nm, 5mW-1W) of SHG crystal * 2 and the combination (430nm, 10mW) of Cr:LiSAF and SHG crystal.

Semiconductor laser, for example KnbO ₃Ring resonator (430nm, 30mW), waveguide type wavelength transform combination, the AlGaAs semiconductor (300nm-450nm, 5mW-30mW) of element and the semi-conductive combination of AlGaAs, InGaAs (380nm-450nm, 5mW-100mW), waveguide type wavelength conversion element and AlGaInP.

Other: pulse laser, for example N ₂Laser (337nm, pulse 0.1-10mJ), XeF (350nm, pulse 10-250mJ).

Wherein, from wavelength performance and cost angle, the AlGaInN semiconductor laser (the InGaN semiconductor laser 400-410nm of commercially available acquisition, 5-3OmW) suitable especially.

About scan exposure pattern, inside surface rotating-cylinder method, outside surface rotating-cylinder method and lithographic plate method lithographic plate presoma exposure sources, can utilize all above-mentioned light sources except that pulse laser as light source as exposure mechanism.In fact, from the angle that the photonasty and the lithographic plate of photosensitive material concerned between the production time, preferred especially following exposure sources.

Change the single beam exposure sources that simple method is used a kind of gas laser or Solid State Laser source according to inside surface.

Use the multiple beam exposure sources of many (10 kinds or more) semiconductor laser according to the lithographic plate method.

Use the multiple beam exposure sources of many (10 kinds or more) semiconductor laser according to the outside surface rotating-cylinder method.

Directly describe in the lithographic plate presoma of type at laser as mentioned above, at photosensitive material photonasty X (J/cm ²), the exposure area S (cm of photosensitive material ²), the energy q (W) of every kind of LASER Light Source, laser count between n and the total exposure time (s) and satisfy equation 1.

XS=nqt (equation 1)

ⅰ) under the situation of inside surface rotating cylinder (single beam) method,

Usually, rotate subsidiary scan length L x (cm), the resolution Z (point/cm) and between the total exposure time t (s) satisfy equation 2 of f (radian per second), photosensitive material at laser.

FZt=Lx (equation 2)

ⅱ) under the situation of outside surface rotating cylinder (multiple beam) method

Usually, (satisfy equation 3 between point/cm), total exposure time t (s) and the laser number (n) at subsidiary scan length L x (cm), the resolution Z of rotating cylinder rotation F (radian per second), photosensitive material.

FZnt=Lx (equation 3)

ⅲ) under the situation of lithographic plate (multiple beam) method

Usually, (satisfy equation 3 between point/cm), total exposure time t (s) and the laser number (n) at subsidiary scan length L x (cm), the resolution Z of the rotation F of mirror polygon (radian per second), photosensitive material.

FZnt=Lx (equation 4)

By the required resolution (2560dpi) of design actual print version, version size (A1/B1,42 inches of subsidiary scan length), photosensitive property (wavelength photoreceptor, the light sensitivity: about 0.1mJ/cm of 20/hour of conditions of exposures and sensitive offset press version presoma of the present invention ²) satisfy above-mentioned formula, can be understood as in photosensitive material of the present invention more preferably semiconductor light beam and multiple beam method combination.And, consider operability, cost etc., the most preferably combination of outside surface rotating-cylinder method and semiconductor laser beam multiple beam exposure sources.

The presoma exposure light source of sensitive offset press version presoma of the present invention can use UHV (ultra-high voltage), high pressure, middle pressure, Cooper-Hewitt lamp, chemical lamp, carbon arc lamp, fluorescent light, tungsten lamp, daylight lamp etc.

Describe the present invention in detail below by embodiment.But scope of the present invention is not limited to this.

Embodiment 1

Make aluminium alloy molten bath contain the trace element shown in the following table 1-2, thereby preparation contain the aluminium alloy molten bath of giving the trace element of amount to some extent respectively with (1)-(5) of composition shown in the following table 1-1.After prepared molten bath filtration, make the thick 500mm of ingot bar, wide 1200mm through the DC casting method respectively.The mean size of 10mm is cut into through planer in the surface of gained ingot bar, then, 550 ℃ of about 5 hours of heating down, carries out immersion treatment respectively.When temperature drops to 400 ℃, these ingot bars are made the rolling plate of thick 2.7mm by using hot-rolling.And, use the continuous annealing machine to heat-treat down at 500 ℃.These annealing versions obtain the aluminium alloy version of thick 0.24mm respectively through cold rolling then.

With of any processing of gained aluminium alloy version through A1-A3 described in the following table 1-3 and B1-B3.In B1 and B2 processing, carry out roughened, use three No. 8 brushes (bristle diameter: 0.5mm) with the float stone suspension with brush.In alkaline etching was handled (1) and (2), the use solution temperature was that 65 ℃ 2.6wt% NaOH and the aluminum ions solution of 6.5wt% are as etching solution.In the electrochemical roughening processing, use 1wt% sulfuric acid and the aluminum ions solution of 0.5wt% as electrolyte, and through AC process.In anodization, the sulfuric acid solution that uses 0.15wt% is as electrolyte, and through Direct current treatment.And the method that contains the acidic group and the primer layer of the polymkeric substance of base according to method described in the EP0904954A2 and formation uses sodium silicate A1 to carry out surperficial control and treatment.Form the method for the primer layer of As colloidal sol leaf according to disclosed method among the flat 9-236911A of JP-.

Preparation has the photosensitive layer coating liquid a-j of following composition respectively, is coated on the above-mentioned substrate them and drying, or through following method, thereby form photographic layer a-j.The composition carbon black dispersion liquid 10.0g4-diazonium-based diphenylamine-formaldehyde condensation products phosphoric acid hexafluoride salt 0.5g methacrylic acid that is used for the coating fluid of photographic layer a, acrylic acid 2-hydroxy methacrylate, the free 5.0g base co-polymer of benzyl methacrylate and vinyl cyanide (mol ratio:15:30:40:15, weight-average molecular weight:100000) malic acid 0.05g fluorine surfactant (trade name " FC-430 "; Being produced by U.S. 3M) the 0.05g1-methoxy-2-propanol 80.0g ethyl lactate 15.0g water 5.0g capric acid 0.03g that forms that is used for the coating fluid of photosensitive layer b has the monomer of phenolic hydroxyl and the copolymer of P-aminobenzene-sulfonamide (mol ratio: 10: 50; 0.75g weight average molecular weight: 500000), p-Cresol novolac resin (, contrast=6/4) 0.25g p-methyl benzenesulfonic acid 0.003g tetrahydrophthalic anhydride 0.03g cyanine dye 0.017g Victoria's ethereal blue (counter ion counterionsl gegenions of BOH are 1-naphthalene sulfonic aicd root anion in this dyestuff) 0.017g surfactant (surfactant trade name " Megafack F-177 "; By Dainippon Ink 0.05g ﹠ amp; Chemicals Inc. produces) gamma-butyrolacton 10.0g methyl ethyl ketone 10.0g1-methoxy-2-propanol 1.0g is used between the composition capric acid 0.03g of coating fluid of photosensitive layer c, p-Cresol novolac resin (, contrast=6/4) 1.0g p-methyl benzenesulfonic acid 0.003g tetrahydrophthalic anhydride 0.03g cyanine dye 0.017g Victoria's ethereal blue (counter ion counterionsl gegenions of BOH are 1-naphthalene sulfonic aicd root anion in this dyestuff) 0.017g surfactant (surfactant trade name " Megafack F-177 "; By Dainippon Ink ﹠ amp; 0.05gChemicalsInc. production) gamma-butyrolacton 10.0g methyl ethyl ketone 10.0g1-methoxy-2-propanol 1.0g is used for the higher linear organic polymer 2.0g sensitizer (λ of sensitization coating fluid tetramethoxy methane tetraacrylate 1.5g molecular weight of photopolymerization layer for the composition of the coating fluid of photosensitive layer d_Max(THF liquid) 479nm, ε=6.9 * 10 ⁴) 0.15g light trigger 0.2g ＂ IRGACURE 907 ＂ (trade name is produced by Ciba-Geigy) 0.4g ε-phthalocyanine dye/linear organic polymer weight polymers dispersion liquid 0.2g fluorine non-ionic surfactant (trade name " Megafack F-177 "; By DainipponInk﹠amp; 0.03gChemicals Inc. production) methyl ethyl ketone 9.0g propylene glycol monomethyl ether acetic acid esters 7.5g toluene 11.0g is used for the coating fluid of oxygen separation layer

3wt% aqueous solution (the saponification degree 98mol% of polyvinyl alcohol (PVA), the degree of polymerization 500) composition that is used for the coating fluid of photographic layer e 20wt% propylene glycol monomethyl ether solution (37.5g is poly-than=80/20 altogether) the dispersible pigment dispersion 13.0g methyl ethyl ketone 74.0g that is used for the coating fluid tetramethylol methane tetraacrylate 2.5g allyl methacrylate/methacrylic acid copolymer of polymer layer be used for photographic layer coating fluid (with the polymer layer coating and dry after coating) saponification degree of 10wt% is 79.5% polyvinyl alcohol water solution (trade name " PVA-405 ", by 10.5gKuraray Co., Ltd. produce) adjuvant (the first 0.41g alcoholic solution of compound [chemical formula 5] described in the 18th page of the flat 9-114043A of 0.11wt% JP-) adjuvant (the first 0.41g alcoholic solution of compound [chemical formula 6] described in the 18th page of the flat 9-114043A of 0.11wt%Jp-) silver halide emulsion (at silver halide emulsion [the 0090]-0.50g[0093 described in the 17th page of the flat 9-114043A of JP-]) surfactant (the water 0.40g solution of compound [chemical formula 7] described in the 19th page of the flat 9-114043A of 5wt%JP-) water 7.80g reductive agent dispersion liquid 1.20g be used for the oxygen separation layer coating fluid (with the photographic layer coating and dry after be coated with) saponification degree of 10wt% is 98.5% polyvinyl alcohol water solution (trade name " PVA-105 ", by 200.0gKuraray Co., Ltd. produce) the aqueous solution 4.0g of alkali presoma dispersion liquid (at the 1.25g dispersion liquid of compound [chemical formula 9] described in the 19th page of the flat 9-114043A of Jp-) the surfactant composition that is used for the coating fluid of photographic layer f is used for the naphthoquinones-1 of the coating fluid acetone-pyrogallol of resin bed, the solution resin 5.0g cresol-formaldehyde resin 10.0g methyl ethyl ketone 150.0g cyclohexanone 122.0g of 2-basudin-(2)-5-sulphonic acid ester is used for coating fluid (with resin bed coating and dry coating afterwards) the chlorine silver bromide gelatin emulsion (Cl:70mol% of photographic layer, Br:30mol%, mean grain size: 0.28 μ m, gelatin amount: 55g in the 1kg 1000.0g emulsion, silver halide content: 0.85mol) 1,3-diethyl-5-[2-(3-(3-sulfo group propyl group) benzoxazole-2-subunit) ethylidene] 2-thiohydantoin sodium salt 50.0ml4-hydroxyl-6-methyl isophthalic acid, 3,3a, 2% aqueous solution 35.0g physical development core layer of 0.5% aqueous slkali 100.0ml4-, two chloro-6-hydroxyl-equal three azines of the 7-purine will be by Carey Lea method preparation silver sol during with dry weight silver content be 5mg/m ²Coating.Silver halide layer (on physical development core layer, being coated with)

The mean grain size that to be made up of 40mol% chloride and 60mol% bromide is 0.3 micron a chlorine silver bromide emulsion (silver salt: gelatin (weight ratio)=1: 1) with 2.0g/m ²Amount coating.The composition that is used for the coating fluid of photographic layer h is used for the coating fluid Fastogen indigo plant 8120 of photoconductive layer, and (the nonmetal phthalocyanine dyestuff is by Dainippon Ink ﹠ amp; Chemicals; 1.0 weight portion Inc. production) copolymer (methacrylic acid 20mol%) 10.0 weight portion oxolanes 60.0 weight portion cyclohexanone 40.0 weight portions of methyl methacrylate and methacrylic acid are for the protection of coating fluid (being coated with at the photoconductive layer) polyvinyl butyral resin (2000-L of layer; Produced by Denki Kagaku Kogyo K.K.) 2.0 weight portion stearic acid, 0.5 parts by weight of ethanol, 97.5 weight portions forming of coating fluid of being used for photosensitive layer i have polymer (at the compound (1) described in the 16th page of 1.0g of the flat 10-207068A of JP-) adjacent naphthoquinones two nitrine-4-sulfonic acid chloride 0.1g dyestuff that produce the functional group of sulfonic acid at side chain, and wherein the counter ion counterionsl gegenions of the blue BOH of Victoria's alcohol replace 0.05g fluorine surfactant (trade name " Megafack F-176PF " with 1-naphthalene sulfonic aicd root anion; By Dainippon Ink ﹠ amp; 0.06gChemicals Inc. production) methyl ethyl ketone 10.0g gamma-butyrolacton 10.0g is used for the composition of the coating fluid of photographic layer j

Form the photographic layer j that silverskin has exposed with the 6th page of described same way as [0049] among the flat 11-139023A of JP-, and according to:

Shown in following table 1-2, by on substrate, carrying out the lithographic plate presoma that different disposal combination substrate comes production example 1-1 to 1-48 and comparative example 1-1 to 1-16 with photographic layer a-j respectively.Then, on these lithographic plate presomas, use different laser to form image, then through the printing test.The image of observation post printing, and estimate the exposure defective (as the exposure evaluation of result in the table) of non-image part.And, on these galleys, can print in a large number but do not reduce on the version of picture quality and estimate the ability stand duplicate printing.And, also estimate the homogeneity of the pit that on substrate surface, forms by roughened.Remove photographic layer and observe the homogeneity that substrate surface is estimated pit from substrate by SEM.The results are shown in following table 1-3 to 1-5.

Relatively estimate the exposure result among the embodiment, the ability that stands duplicate printing and pit homogeneity by the exposure result among the comparative example, the ability that stands duplicate printing and pit homogeneity, version among the comparative example is that the mode identical with these embodiment produced, and does not just contain trace element.In following table 1-3 to 1-5, the numerical value that stands in the ability hurdle of duplicate printing in evaluation shows, stands the ability of duplicate printing 100 times corresponding to comparative example's the ability that stands duplicate printing (the version number that can print) in an embodiment.

Table 1-1

Component	Alwt％	Siwt％	Fewt％	???Cuwt％	???Mnwt％	???Mgwt％	???Znwt％	???Tiwt％
									????(1)	99.620	????0.06	????0.30	????0.017	????0.001	????0.001	????0.001	????0.03
????(2)	99.452	????0.15	????0.35	????0.006	????0.001	????0.010	????0.001	????0.03
									????(3)	99.537	????0.1	????0.3	????0.02	????0.001	????0.015	????0.001	????0.03
????(4)	99.796	????0.03	????0.10	????0.03	????0.001	????0.002	????0.001	????0.01
									????(5)	99.268	????0.15	????0.5	????0.03	????0.001	????0.02	????0.001	????0.03

Table 1-2

Disposal route	The brush roughening	Alkaline etching is handled (1)	Going does not have optical processing	The electrochemical roughening processing	Alkaline etching is handled (2)	Going does not have optical processing	Anodization	The surface control and treatment	The primer layer
										A1	Do not have	Al solution amount 5.5g/m 2	The nitric acid spraying	Magnitude of current 270C/dm 2	Al solution amount 0.2g/m 2	The sulfuric acid spraying	Coating weight 2.6g/m 2	Sodium silicate is handled	The polymkeric substance that contains base and acidic group
A2	With top identical	With top identical	With top identical	With top identical	With top identical	With top identical	With top identical	Do not have	Sol solutions
										A3	With top identical	With top identical	With top identical	With top identical	With top identical	With top identical	With top identical	Do not have	Do not have
B1	Do not have	Al solution amount 8g/m 2	The nitric acid spraying	Magnitude of current 180C/dm 2	Al solution amount 1.0g/m 2	The sulfuric acid spraying	Coating weight 2.4g/m 2	Do not have	Siliatin
											Do not have	With top identical	With top identical	With top identical	With top identical	With top identical	With top identical	Do not have	Beta-alanine

Table 1-3

	Solvent	Trace element		The treatment conditions of substrate	Photographic layer	Exposure result's evaluation	Stand the ability assessment of duplicate printing	The tight contact of photographic layer	The pit homogeneity
										The element kind	Addition (ppm)
		Embodiment 1-1	????(1)									????Li	????10	????A1	????b	Good	????110	Good	Good
Embodiment 1-2	????(1)			????Na	????10	????A1	????b	Good	????112	Good	Good
		Embodiment 1-3	????(1)									????K	????10	????A1	????b	Good	????108	Good	Good
Embodiment 1-4	????(1)			???Rb	????10	????A1	????b	Good	????110	Good	Good
		Embodiment 1-5	????(1)									????Cs	????10	????A1	????b	Good	????110	Good	Good
Embodiment 1-6	????(1)			????Ca	????10	????A1	????b	Good	????112	Good	Good
		Embodiment 1-7	????(1)									????Sr	????10	????A1	????b	Good	????110	Good	Good
Embodiment 1-8	????(1)			????Ba	????10	????A1	????b	Good	????108	Good	Good
		Embodiment 1-9	????(1)									????Sc	????10	????A1	????b	Good	????110	Good	Good
Embodiment 1-10	????(1)			????Y	????10	????A1	????b	Good	????108	Good	Good
		Embodiment 1-11	(1)									????Nb	????10	????A1	????b	Good	????111	Good	Good
Embodiment 1-12	????(1)			????Ta	????10	????A1	????b	Good	????110	Good	Good
		Embodiment 1-13	????(1)									???Mo	????10	????A1	????b	Good	????109	Good	Good
Embodiment 1-14	????(1)			????W	????10	????A1	????b	Good	????108	Good	Good
		Embodiment 1-15	????(1)									????Tc	????10	????A1	????b	Good	????108	Good	Good
Embodiment 1-16	????(1)			????Re	????10	????A1	????b	Good	????110	Good	Good
		Embodiment 1-17	????(1)									????Ru	????10	????A1	????b	Good	????110	Good	Good

Embodiment 1-18	(1)	????Os	????10	????A1	????b	Good	????110	Good	Good
										Embodiment 1-19	(1)	????Rh	????10	????A1	????b	Good	????108	Good	Good
Embodiment 1-20	(1)	????Ir	????10	????A1	????b	Good	????108	Good	Good
										Embodiment 1-21	(1)	????Pd	????10	????A1	????b	Good	????110	Good	Good
Embodiment 1-22	(1)	????Pt	????10	????A1	????b	Good	????112	Good	Good
										Embodiment 1-23	(1)	????Ag	????10	????A1	????b	Good	????112	Good	Good
Embodiment 1-24	(1)	????Au	????10	????A1	????b	Good	????112	Good	Good
										Embodiment 1-25	(1)	????C	????10	????A1	????b	Good	????109	Good	Good
Embodiment 1-26	(1)	????Ge	????10	????A1	????b	Good	????110	Good	Good
										Embodiment 1-27	(1)	????P	????10	????A1	????b	Good	????111	Good	Good
Embodiment 1-28	(1)	????As	????10	????A1	????b	Good	????110	Good	Good
										Embodiment 1-29	(1)	????S	????10	????A1	????b	Good	????108	Good	Good
Embodiment 1-30	(1)	????Se	????10	????A1	????b	Good	????110	Good	Good
										Embodiment 1-31	(1)	????Te	????10	????A1	????b	Good	????108	Good	Good
Embodiment 1-32	(1)	????Po	????10	????A1	????b	Good	????112	Good	Good
										Embodiment 1-33	(1)	????Mo	????100	????A1	????b	Good	????115	Good	Good
Embodiment 1-34	(2)	????Mo	????10	????A1	????b	Good	????111	Good	Good
										Comparative example 1-1	(1)	Do not have	????-	????A1	????b	Difference	????100	Be on duty mutually	Be on duty mutually
Comparative example 1-2	(2)	Do not have	????-	????A1	????b	Difference	????95	Be on duty mutually	Be on duty mutually

Table 1-4

	Solvent	Trace element		The treatment conditions of substrate	Photographic layer	Exposure result's evaluation	Stand the ability assessment of duplicate printing	The tight contact of photographic layer	The pit homogeneity
										The element kind	Addition (ppm)
		Embodiment 1-35	(1)									Na,W	Total amount 3	A1	?b	Good	????110	Good	Good
Embodiment 1-36	(2)			Na,W	Total amount 3	A1	?b	Good	????105	Good	Good
		Embodiment 1-37	(3)									Na,W	Total amount 3	A1	?b	Good	????115	Good	Good
Embodiment 1-38	(4)			Na,W	Total amount 3	A1	?b	Good	????102	Good	Good
		Embodiment 1-39	(5)									Na,W	Total amount 3	A1	?b	Good	????115	Good	Good
Comparative example 1-3	(1)			Do not have	???-	A1	?b	Difference	????100	Be on duty mutually	Be on duty mutually
		Comparative example 1-4	(2)									Do not have	???-	A1	?b	Difference	????95	Be on duty mutually	Be on duty mutually
Comparative example 1-5	(3)			Do not have	???-	A1	?b	Difference	????105	Be on duty mutually	Be on duty mutually
		Comparative example 1-6	(4)									Do not have	???-	A1	?b	Difference	????90	Difference	Inhomogeneous
Comparative example 1-7	(5)			Do not have	???-	A1	?b	Difference	????90	Difference	Inhomogeneous

Table 1-5

	Solvent	Trace element		The treatment conditions of substrate	Photographic layer	Exposure result's evaluation	Stand the ability assessment of duplicate printing	The tight contact of photographic layer	The pit homogeneity
										The element kind	Addition (ppm)
		Embodiment 1-40	(3)									Na,W	Total amount 3	????B1	????a	Good	????115	Good	Good
Comparative example 1-8	(3)			Do not have	???-	????B1	????a	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-41	(3)									Na,W	Total amount 3	????A2	????d	Good	????110	Good	Good
Comparative example 1-9	(3)			Do not have	???-	????A2	????d	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-42	(3)									Na,W	Total amount 3	????B2	????h	Good	????110	Good	Good
Comparative example 1-10	(3)			Do not have	???-	????B2	????h	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-43	(3)									Na,W	Total amount 3	????A1	????c	Good	????115	Good	Good
Comparative example 1-11	(3)			Do not have	???-	????A1	????c	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-44	(3)									Na,W	Total amount 3	????A3	????e	Good	????110	Good	Good
Comparative example 1-12	(3)			Do not have	???-	????A3	????e	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-45	(3)									Na,W	Total amount 3	????A3	????e	Good	????110	Good	Good
Comparative example 1-13	(3)			Do not have	???-	????A3	????e	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-46	(3)									Na,W	Total amount 3	????B2	????f	Good	????110	Good	Good
Comparative example 1-14	(3)			Do not have	???-	????B2	????f	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-47	(3)									Na,W	Total amount 3	????B2	????i	Good	????110	Good	Good
Comparative example 1-15	(3)			Do not have	???-	????B2	????i	Difference	????100	Be on duty mutually	Be on duty mutually
		Embodiment 1-48	(3)									Na,W	Total amount 3	????A3	????j	Good	????108	Good	Good
Comparative example 1-16	(3)			Do not have	???-	????A3	????j	Difference	????100	Be on duty mutually	Be on duty mutually

Embodiment 2

Embodiment 2-1 to 2-8 and comparative example 2-1 to 2-2

Preparation contains the molten bath of the aluminium alloy of following element and aluminium.

Si:0.06wt％

Fe:0.30wt％

Cu:0.017wt％

Mn:0.001wt％

Mg:0.001wt％

Zn:0.001wt％

Ti:0.03wt％

After above-mentioned A1 molten bath filtration purification, preparing thickness by the DC casting method is that 500mm and width are the ingot bar of 1200mm.It is 10mm that mean size is cut into by planer in the surface of gained ingot bar.Then, under 550 ℃, they were soaked about 5 hours, when temperature drops to 400 ℃, these ingot bars are made the rolling plate of thick 2.7mm by using hot-rolling.And, use the continuous annealing machine to heat-treat down at 500 ℃.By cold-rolling mill these annealing versions are made the aluminium alloy version of thick 0.24mm then.As the Rolling roller of cold-rolling mill, use roller with different surface roughness, have the aluminium alloy version of different mean roughness by carrying out cold rolling production at reverse side (with the surperficial facing surfaces that forms photographic layer).

Then, (aluminum solutions amount: 5.5g/m is handled through alkaline etching in the front (not passing through the surface of roughening in above-mentioned cold-rolling treatment) of different aluminum alloys version ²), then handled through the past unglazed (Death matt) by the nitric acid spraying.At 270C/dm ²The magnitude of current under carry out the alternating current electrolysis roughened, thereby make this surface roughening.Then, carry out alkaline etching again and handle (aluminum solutions amount: 0.2g/m ²), and by nitric acid spraying go do not have optical processing.And, use anodizing apparatus on the pro and con of aluminium alloy, to form anodic film (the film quantity on the front: 2.6g/m with structure shown in Figure 3 ², the film quantity on the reverse side: 0.1g/m ²).Then, use sodium silicate to carry out interface processing, then, use the polymkeric substance that contains base and acidic group to form primer layer (according to the method described in the EP0904954A2) in the front.

Like this, produced the substrate that is used for the lithographic plate presoma, the reverse side of described substrate has different surfacenesses.

Then, the photosensitive layer coating liquid that will have following composition is coated on the primer layer of substrate of the lithographic plate presoma of being produced and is dry, thereby obtains the lithographic plate presoma.Described lithographic plate presoma is of a size of 650mm * 550mm.

The composition capric acid 0.03g that is used for the coating fluid of photographic layer has the monomer of phenolic hydroxyl and the multipolymer of P-aminobenzene-sulfonamide (mol ratio: 50: 50, heavy 0.75g average molecular weight: 500000), the p-Cresol novolac resin (, contrast=6/4) 0.25g p-toluenesulfonic acid 0.003g tetrahydrophthalic anhydride 0.03g cyanine dye 0.017g Victoria's ethereal blue (counter ion counterionsl gegenions of BOH are 1-naphthalene sulfonic aicd root negative ion in this dyestuff) 0.017g surfactant (surfactant, trade name " MegafackF-177 "; By DainipponInk 0.05g﹠amp; Chemicals Inc. produces) gamma-butyrolacton 10.0g methyl ethyl ketone 10.0g1-methoxyl-2-propyl alcohol 1.0g

Transport each sample of the lithographic plate presoma that is produced by travelling belt, and estimate the generation of sliding in transporting and the existence of distortion is with or without.In following table 2-1, shown evaluation result." Surfcom " that produce by TokyoSeimitsu K.K. is determined at substrate reverse side upper edge average surface roughness (following examples 2-9 is identical) longitudinally.In table 2-1, " zero " in the slip value column illustrate and slides, and " △ " illustrate slightly slip of generation, and still, it is in permissible range, and " * " illustrates frequently and slide." zero " illustrate and is distorted in the distortion value column, and " △ " illustrate and take place slightly to twist, and still, it is in permissible range, and " * " illustrates frequently and be distorted.Same tag is suitable among the following table 2-2.

Table 2-1

	Average surface roughness (Ra)		μm	Slide and estimate	Wriggle and estimate
						Laterally (Ral)	Vertically (Ras)	Ral/Ras
	Embodiment 2-1	????0.19	????0.17						????1.12	????△	????△
????1.14				????0.40	????0.35		????○	????○
	Embodiment 2-3	????0.40	????0.21						????1.90	????○	????○
Embodiment 2-4				????0.30	????0.18	????1.67	????○	????○
	Embodiment 2-5	????0.16	????0.14						????1.14	????○	????○
Embodiment 2-6				????0.24	????0.10	????2.40	????○	????○
	Embodiment 2-7	????0.30	????0.10						????3.00	????○	????○
Embodiment 2-8				????0.17	????0.11	????1.55	????○	????○
	Comparative example 2-1	????0.25	????0.24						????1.04	????×	????×
Comparative example 2-2				????0.28	????0.28	????1.00	????×	????×

Embodiment 2-9 to 2-11 and comparative example 2-3

Preparation contains the molten bath of the aluminium alloy of following element and aluminium.

Si:0.10wt％

Fe:0.30wt％

Cu:0.02wt％

Mn:0.001wt％

Mg:0.015wt％

Zn:0.001wt％

Ti:0.03wt％

After above-mentioned A1 molten bath filtration purification, preparing thickness by the DC casting method is that 500mm and width are the ingot bar of 1200mm.It is 10mm that mean size is cut into by planer in the surface of gained ingot bar.Then, under 550 ℃, they were soaked about 5 hours, when temperature drops to 400 ℃, these ingot bars are made the rolling plate of thick 2.7mm by using hot-rolling.And, use the continuous annealing machine to heat-treat down at 500 ℃.By cold-rolling mill these annealing versions are made the aluminium alloy version of thick 0.24mm then.In cold rolling, use Rolling roller, and be 0.17 along the horizontal mean roughness of (Ral) with given pattern, average surface roughness longitudinally (Ras) is 0.16 (Ral/Ras=1.06).

To stand the alkaline etching processing with the aluminium alloy version that the same way as of embodiment 2-1 is produced and go not have optical processing.Then, at 300C/dm ²The magnitude of current under on the front of aluminium alloy version, carry out the electrochemical roughening processing.This processing is performed such: the part line of electric force arrives reverse side, longitudinally carries out slight electrochemical roughening processing with the band forms of the given width at two ends from the negative.And, exist the thickness condition in the space of electrolysis differently to change roughening width on the reverse side by changing at reverse side.The result of electrochemical roughening processing, this surface has the average surface roughness of 0.40 μ m, has the average surface roughness Ra of 0.30 μ m in the given area of reverse side end.

Moreover, carry out alkaline etching and handle (aluminum solutions amount: 0.2g/m ²), and by nitric acid spraying go do not have optical processing.And, use anodizing apparatus on the pro and con of aluminium alloy, to form anodic film (the film quantity on the front: 2.6g/m with structure shown in Figure 4 ², the film quantity on the reverse side: 0.1g/m ²).Then, use sodium silicate to carry out interface processing, then, use the polymkeric substance that contains base and acidic group to form primer layer (according to the method described in the EP0904954A2) in the front.

Like this, produced the substrate that is used for the lithographic plate presoma, the reverse side of described substrate has the slight rough region of different in width.

Form photographic layer with the same way as of embodiment 2-1, and slide and wriggle evaluation with the same way as of embodiment 2-1.Evaluation result is shown among the following table 2-2.

Table 2-2

	The reverse side roughening		Slide and estimate	Wriggle and estimate
					Width (mm)	Average surface roughness (Ra) μ m
	Embodiment 2-9	????10					????0.30	????○	????○
Embodiment 2-10			????25	????0.31	????○	????○
	Embodiment 2-11	????50					????0.30	????○	????○
Comparative example 2-3			????0.5	????0.30	????×	????×

Then, prepare the lithographic plate presoma, do not cut, rolled and preserve 2 weeks with coil form with the same way as of embodiment 2-1 and embodiment 2-9.Same way as with embodiment 2-1 and embodiment 2-9 is made, but the amount of the oxide film on reverse side is 0.05g/m ²Lithographic plate presoma (embodiment 2-1 ' and embodiment 2-9 ') do not cut equally, rolled and preserve 2 weeks with coil form respectively again.

Measure the photographic layer of above-mentioned four kinds of lithographic plate presomas by the scoring test machine with same structure shown in Figure 5, the result produces the obvious visible scratch of 30g.

After preserving for 2 weeks, again they are launched, longitudinally be cut into the size of 800mm, and make 1000 lithographic plate presomas.Observe the surface of every photographic layer, result's average scratch ratio on 1000, the amount of the oxide film on reverse side is 0.1g/m ²Sheet in be 0.1/ (embodiment 1 and embodiment 9), the amount of the oxide film on reverse side is 0.05g/m ²Sheet in be 4.8/ (embodiment 2-1 ' and embodiment 2-9 ').

Therefore, confirmed and on the reverse side of substrate, to have formed 0.1g/m effectively ²Or above anodic film, thereby prevented the scratch on the photographic layer of substrate reverse side in the storage.

The preparation method of embodiment 3 embodiment 3-1 to 3-4 and comparative example 3-1,3-2 substrate

Use and mainly to form and to contain Si:0.07wt% by aluminium, Fe:0.30wt%, Cu:0.17wt%, Mn:0.001wt%, Mg:0.001wt%, Zn:0.001wt%, Ti:0.03wt% and the alloy that can ignore impurity prepare molten bath.Handle and filter through molten bath, then, preparing thickness by the DC casting method is that 500mm and width are the ingot bar of 1200mm, then, it is 10mm that mean size is cut into by planer in the surface of gained ingot bar, then, under 550 ℃, they were soaked about 5 hours, when temperature drops to 400 ℃, these ingot bars are made the rolling plate of thick 2.7mm by using hot-rolling, and, use the continuous annealing machine to heat-treat down at 500 ℃, then by the cold rolling aluminium alloy version of these annealing versions being made thick 0.24mm.This aluminium plate width is controlled at 1030mm, then, carries out following surface treatment continuously.

(a) mechanically roughened processing

Use equipment shown in Fig. 6, the rotation nylon bruss by roll form carries out mechanically roughened, adds proportion simultaneously and be 1.12 brilliant polish (float stone and silica sand) suspending liquid and water on the aluminium plate surface as polishing slurries.The mean grain size of brilliant polish is 40-45 μ m, and maximum particle diameter is 200 μ m.Use the material of 6.10 nylon as nylon bruss, staple length 50mm, diameter are 0.3mm.In this nylon bruss, these maos are transplanted in the hole that on the stainless pipe of φ 330mm, makes densely.Use 3 rotating brushes.The distance that is positioned between two load bearing rollers (φ 200mm) of brushing the bottom is 300mm.Make the brush roll pressurized, the high 7KW of load before the load ratio brush roll of the drive motor that makes the brush rotation is pressed on the aluminium plate.The sense of rotation of brush is identical with the moving direction of aluminium, and rotates with 200rpm.(b) etch processes of usefulness alkaline reagent

By spraying concentration down at 70 ℃ is the NaOH of 2.6wt% and the aluminium ion etching aluminium plate that concentration is 6.5wt%, is 13g/m thereby make the meltage of aluminium plate ²Then, carry out the water flushing by spraying.(c) go not have optical processing

Aqueous solution of nitric acid (containing the 0.5wt% aluminium ion) by spraying 1wt% under 30 ℃ temperature goes not have optical processing, then, carries out the water flushing by spraying.Use aforesaid aqueous solution of nitric acid going not have in the optical processing, come in the comfortable aqueous solution of nitric acid to carry out waste liquid in the method for electrochemical rougheningization with alternating current.(d) electrochemical roughening processing

Use the alternating current of 60Hz to carry out the electrochemical roughening processing continuously.Electrolyte in this processing is the aqueous solution of nitric acid (containing 0.5wt% aluminium ion and 0.007wt% ammonium ion) of the 1wt% under 50 ℃.AC power waveform is shown in Fig. 2, and electric current is 2 milliseconds from the zero time T P that is increased to peak value, and duty factor is 1: 1, uses trapezoidal shortwave alternating current, and uses carbon electrode as counter electrode: carry out the electrochemical roughening processing under these conditions.Use ferrite as auxiliary electrode.Use two electrolytic vessels shown in Figure 3.Current density when current peak is 30A/dm ², the magnitude of current adds up to 250C/dm when aluminium plate is used as anode ²In impressed current anode, 5% current segment ground passes through from power supply.

Carry out the water flushing by spraying then.(e) etch processes

By spraying concentration under 70 ℃ temperature is the NaOH of 2.6wt% and the aluminium ion etching aluminium plate that concentration is 6.5wt%, is 13g/m thereby make the meltage of aluminium plate ²The dirty component of mainly being made up of aluminium hydroxide that will produce in the time of will using alternating current to carry out electrochemical roughening in the above-mentioned stage is removed, and the marginal portion of the pit that produced is dissolved, thereby makes the marginal portion smooth.Carry out the water flushing by spraying then.(f) go not have optical processing

Go not have optical processing by the aqueous sulfuric acid (containing the 0.5wt% aluminium ion) that sprays the 25wt% under 60 ℃, then, carry out the water flushing by spraying.

(g) anodization

By using the two stepping material electrolysis mode anodization equipment (length of the first time and the electrolysis section second time: respectively be 6m with structure shown in Figure 7, the length of feeding part: 3m for the first time, the length of feeding part: 3m for the second time, for the first time and for the second time length of feed electrode: respectively be 2.4m) be that the sulfuric acid concentration (containing the 0.5wt% aluminium ion) of 100g/l, 50 ℃ temperature, 1.1 proportion and the conductivity of 0.39S/cm are carried out anodization with the electrolysis section.Then, carry out the water flushing through spraying.

In this step, in anodization equipment, be installed in the feed electrode 65a first time on the feeding part 62a for the first time from the current direction of power supply 67a and 67b, the process electrolyte flow is to aluminium plate, electrolysis section 63a is on the surface of aluminium plate and forms oxide film in the first time, and, get back to power supply by being installed in electrolysis electrode 66a and the 66b on the feeding part 63 first time.

On the other hand, be installed in the feed electrode 65b second time on the feeding part 62b for the second time from the current direction of power supply 67a and 67b, and in the same manner, the process electrolyte flow is to aluminium plate, electrolysis section 63b is on the surface of aluminium plate and forms oxide film in the second time, and the magnitude of current that is fed to feeding part 2a for the first time from power supply 67a and 67b equates with the magnitude of current that is fed to the feeding part 2b second time from power supply 67c and 67d, and the second time feeding part 62b the charging current density of oxide film be about 23 (D/dm ²).At the feeding part 62b second time, be 1.2g/m by oxide film ²Surperficial inflow current.Final oxide film amount is 2.4g/m ²

Stand to be called [A] up to the substrate of this phase process.

In substrate [A], the substrate of making through brush polishing step (a) is not called substrate [B].

In substrate [A], bristle diameter is that the substrate of 0.48mm is called substrate [C].

In substrate [B], on the negative electrode that carries out the electrochemical roughening processing with 100C/dm ²The substrate that obtains is called substrate [D].

Under the described condition of following table 3-1, on above-mentioned gained substrate, carry out the long-pending aftertreatment of control surface, thereby the surface area that makes substrate is controlled at 2-30 times of unit area, and the photographic layer shown in the preparation table 3-1 on the gained substrate, thereby the lithographic plate presoma of production example 3-1 to 3-4.

Presuppose physisorption, calculate the surface area of substrate by the Canta Sorb of Yuasa Ionics K.K. production by the adsorbance of the mixed gas of helium and krypton.

Specifically, will cut into 25 through the substrate sample of above-mentioned processing, each sheet is of a size of 60mm * 2mm, places it in the U type pipe and heat under 180 ℃ under dried nitrogen environment to outgas in 60 minutes.Then, the U type pipe that will contain this sample is placed on and locates, it is immersed in the liquid nitrogen cools off, simultaneously with constant flow rate by above-mentioned adsorbed gas.After adsorbed gas stream is constant, in this U type pipe immersion tap water at room temperature, when sample temperature is got back to atmospheric temperature, measure the adsorbed gas scale of construction that produces,, use calibration curve to calculate its surface area by the BET fix point method as the electric signal of change in flow.For example, when one that handles aluminium substrate when surperficial, under the situation of above-mentioned sample area, the apparent area of working sample (unit area) is 60mm * 2mm * 25=3000mm ²If, above-mentioned mensuration and reference area S (mm ²) expression, specific surface area is (S/3000).Amass calculated specific surface area by this real mensuration surface area and apparent surface as mentioned above, and in following table 3-1, description is arranged.Form the primer layer

With the coating of following primer solution, 80 ℃ under,, obtain a substrate with 15 seconds of this coated film drying.The coating weight of dry back coated film is 15mg/m ²The polymkeric substance 0.3g methyl alcohol 100g water 1g that primer solution is following Molecular weight: 28000

Next, prepare following photosensitive layer coating liquid, and it is applied on the initiation substrate, making coating weight is 1.8g/m ²Thereby, the lithographic plate presoma of acquisition embodiment 3-1 to 3-4.And, in above-mentioned substrate [A] and [D], form identical photographic layer, do not carry out the aftertreatment that control surface is handled, thereby obtain the lithographic plate presoma of comparative example 3-1 and 3-2.Between following specific copolymer 1 0.75g of photosensitive layer coating liquid 1 capric acid 0.03g, the p-Cresol novolac resin (, contrast=6/4, weight-average molecular weight 3500, the unreacted cresols that contains 0.5wt% 0.25g) p-toluenesulfonic acid 0.003g tetrahydrophthalic anhydride 0.03g cyanine dye A (having following structures) 0.017g dyestuff, wherein the counter ion counterionsl gegenions of Victoria's pure blue B OH are 1-naphthalene sulfonic aicd root negative ion 0.015g fluorine surfactant (surfactant, trade name MegafackF-177; By Dainippon Ink ﹠amp; 0.05gChemicalsInc. produce) gamma-butyrolacton 10g methyl ethyl ketone 10g1-methoxyl 2-propyl alcohol 1g cyanine dye A Synthesizing of specific copolymer 1

In the 500ml three-neck flask that is equipped with stirrer, condenser and tap funnel, add the methacrylic acid of 31.0g (0.36mol), ethyl chloroformate and the 200ml vinyl cyanide of 39.1g (0.36mol), in the ice-water bath cooling, this potpourri is stirred.In 1 hour, from tap funnel, add 36.4g (0.36mol) triethylamine to this potpourri.Add after the end, ice-water bath is removed, and at room temperature this potpourri was stirred 30 minutes.

In this reaction mixture, add 51.7g (0.30mol) P-aminobenzene-sulfonamide, under 70 ℃ with in the oil bath heating this potpourri being stirred 1 hour.Reaction is poured this potpourri in 1 premium on currency that does not stop stirring into after finishing, and the gained potpourri was stirred 30 minutes.This potpourri is removed by filter the precipitation of slurries and 500ml water generates, then, with this dope filtration, with the gained solid drying, obtain white solid N-(to the aminosulfonyl phenyl) Methacrylamide (output, 46.9g).

Then, in the 20ml three-neck flask that is equipped with stirrer, condenser and tap funnel, add N-(to the aminosulfonyl phenyl) Methacrylamide of 4.61g (0.0192mol), the Jia Jibingxisuanyizhi of 2.94g (0.0258mol), vinyl cyanide and the 20gN of 0.80g (0.015mol), the N-dimethyl acetamide, stir this potpourri, heat with hot bath simultaneously.In this potpourri, add 0.15g V-65 (producing), flow down at nitrogen this potpourri was stirred 2 hours, remain on 65 ℃ simultaneously by Wako Pure ChemicalIndustries Ltd..In 2 hours, in this potpourri, add 4.61g N-(to the aminosulfonyl phenyl) Methacrylamide, 2.94g Jia Jibingxisuanyizhi, 0.80g vinyl cyanide and the aforesaid V-65 of 0.15g again by tap funnel.Add after the end, under 65 ℃, again the gained potpourri was stirred 2 hours.After reaction finishes, add in this potpourri 40g methyl alcohol and cooling, the gained potpourri is poured in 2 premium on currency that do not stop stirring, and this potpourri was stirred 30 minutes, then, remove by filter precipitation, and dry, obtain the 15g white solid.Weight-average molecular weight (polystyrene standard) by gel permeation chromatography specific copolymer 1 is determined as 3000.

Table 3-1

	Substrate	??Ra (μm)	Specific surface area	Sensitivity
					Embodiment 3-1	Handle the substrate that obtains by on substrate B, carrying out the steam under pressure micropore sealing described in the flat 4-176690A embodiment 1 of JP-	0.30	????15	?120mJ/cm 2
Embodiment 3-2	Under the atmospheric pressure of ion exchange water, pass through substrate B is soaked the substrate that obtain 30 seconds in boiling water	0.30	????10	?110mJ/cm 2
					Embodiment 3-3	Handle the substrate that obtains by on substrate A, carrying out the steam under pressure micropore sealing described in the flat 4-176690A embodiment 1 of JP-	0.48	????10	?100mJ/cm 2
Embodiment 3-4	Handle the substrate that obtains by on substrate C, carrying out the steam under pressure micropore sealing described in the flat 4-176690A embodiment 1 of JP-	0.23	????10	?100mJ/cm 2
					Comparative example 3-1	Substrate B	0.30	????50	?150mJ/cm 2
Comparative example 3-2	Substrate D	0.55	????50	?140mJ/cm 2

The evaluation of sensitivity

Is 17 μ m (1/es as 500mW, wavelength as 830nm and beam diameter by using output quantity ²) the semiconductor laser lithographic plate presoma exposure that will obtain as mentioned above with the main operation speed of 5m/s, then, by by Fuji Photo Film Co., the PS version developer that Ltd. produces (trade name: developed for 30 seconds by dilution DP-4) (1: 8) aqueous solution.

Form after the image as mentioned above, with Fuji Photo Film Co., Ltd. the just deletion liquid PR-1S of Sheng Chaning is placed on the solid-state image part, before removing, the water flushing under 25 ℃, left standstill 1 minute, the difference of measuring bonding agent reservation amount between deletion by development treatment and the non-image part by scattered reflection under 280nm is as absorption difference, and it is defined as the reservation film.The minimum version surface energy that reservation film amount is increased before rapidly is defined as sensitivity.The result is described among the table 3-1 together.

Find out that from the result of table 3-1 in any lithographic plate presoma of the controlled the present invention of the surface area of aluminium substrate, sensitivity is good, produce the reservation film, and form excellent images.Embodiment 3-5,3-6, comparative example 3-3

On substrate that in embodiment 3-1, obtains under the condition described in the following table 3-2 [A] and substrate [B], carry out the long-pending aftertreatment of control surface, to obtain surface area to be controlled at the substrate of 2-30 times of unit area, and form following photographic layer, thereby the lithographic plate presoma of production example 3-5 and 3-6.Directly go up and form following recording layer, thereby obtain the lithographic plate presoma of comparative example 3-3 at substrate [A].The formation of primer layer

Following primer liquid is applied on the aluminium plate, and 80 ℃ of following dry 30 seconds.Dried coating weight is 10mg/m ²Primer liquid Beta-alanine 0.1g phenyl-phosphonic acid 0.05g methyl alcohol 40g pure water 60g

Next, prepare following photosensitive layer coating liquid, and with this solution coat to above-mentioned initiation aluminium plate, 100 ℃ dry 1 minute down, thereby obtain negative lithographic plate presoma [G-1].Dried coating weight is 1.5g/m ²Photosensitive layer coating liquid 2 fluorinated copolymers (P-8) 0.05g acid agents [SH-1] 0.3g crosslinking chemical 0.5g binder polymers [BP-1] 1.5g infrared absorbing agents [IK-1] 0.07gAIZEN SPILON BLUE C-RH (trade name, by Hodogaya Chemical Co., Ltd. 0.035g produces) fluorine surfactant (trade name " MegafackF-177 "; By Dainippon Ink ﹠amp; Chemicals 0.01gInc. produces) methyl ethyl ketone 12g methyl alcohol 10g1-methoxyl-2-propyl alcohol 8g

Used binder polymer [BP-1] is the illustration compound [BP-1] of above-mentioned polymkeric substance in the photosensitive layer coating liquid 2, and the structure of used fluorinated copolymer (P-8), acid agent [SH-1] and infrared absorbing agents [IK-1] is as follows.

Table 3-2

	Substrate	Ra (μm)	Specific surface area	Sensitivity
					Embodiment 3-5	Handle the substrate that obtains by on substrate A, carrying out the steam under pressure micropore sealing described in the flat 4-176690A embodiment 1 of JP-	0.48	????15	?90mJ/cm 2
Embodiment 3-6	Under the atmospheric pressure of ion exchange water, pass through substrate B is soaked the substrate that obtain 30 seconds in boiling water	0.30	????10	?80mJ/cm 2
					Comparative example 3-3	Substrate A	0.48	????50	?120mJ/cm 2

The evaluation of sensitivity

The negative lithographic plate presoma [G-1] of gained is scanned and exposure for the ultrared semiconductor laser of about 820-850nm by emission wavelength.After the exposure, should version 110 ℃ of following 30 seconds of heating, then, by by Fuji Photo Film Co., the developer solution DP-4 (trade name, 1: 8 dilution) that Ltd. produces develops.In this step, can see with the naked eye that the minimum version surface energy that evenly forms the solid-state image part on whole surface is defined as sensitivity.The results are shown among the table 3-2.

Find out that from the result of table 3-2 in any lithographic plate presoma of the controlled the present invention of the surface area of aluminium substrate, sensitivity is good, produce the reservation film, and form excellent images.

Embodiment 4

Prepare Al molten bath composed of the following components, treated and filter, then, preparing thickness by the DC casting method is that 500mm and width are the ingot bar of 1200mm, then, it is 10mm that mean size is cut into by planer in the surface of gained ingot bar, then, under 550 ℃, they were soaked about 5 hours, when temperature drops to 400 ℃, these ingot bars are made the rolling plate of thick 2.7mm by using hot-rolling, and, use the continuous annealing machine to heat-treat down at 500 ℃, then, by the cold rolling aluminium alloy version of these annealing versions being made thick 0.24mm.This aluminium plate is used for following examples of the present invention and comparative example.Use the solvent of Al to be shown among the table 4-1.Except as otherwise noted, the number percent of following examples all by weight.

Table 4-1

Component	????Si	????Fe	????Cu	????Mn	????Mg	????Zn	????Ti
									?0.06	?0.30	?0.017	?0.001	?0.015	?0.001	?0.03

The aluminium plate of Zhi Bei thick 0.24mm and wide 1030mm is through handling continuously as mentioned above.(a) use known mechanical roughening equipment, the rotation nylon bruss by roll form carries out mechanically roughened, adds proportion simultaneously and be 1.12 brilliant polish (silica sand) suspending liquid and water on the aluminium plate surface as polishing slurries.The mean grain size of brilliant polish is 40-45 μ m, and maximum particle diameter is 200 μ m.Use the material of 6.10 nylon as nylon bruss, staple length 50mm, diameter are 0.3mm.In this nylon bruss, these maos are transplanted in the hole that on the stainless pipe of φ 330mm, makes densely.Use 3 rotating brushes.The distance that is positioned between two load bearing rollers (φ 200mm) of brushing the bottom is 300mm.Make the brush roll pressurized, the high 7KW of load before the load ratio brush roll of the drive motor that makes the brush rotation is pressed on the aluminium plate.The sense of rotation of brush is identical with the moving direction of aluminium, and rotates with 200rpm.(b) being the NaOH of 2.6wt% and the aluminium ion etching aluminium plate that concentration is 6.5wt% by spraying concentration down at 70 ℃, is 13g/m thereby make the meltage of aluminium plate ²Then, carry out the water flushing by spraying.(c) aqueous solution of nitric acid (containing the 0.5wt% aluminium ion) by spraying 1wt% under 30 ℃ temperature goes not have optical processing, then, carries out the water flushing by spraying.Use aforesaid aqueous solution of nitric acid going not have in the optical processing, use in the comfortable aqueous solution of nitric acid with alternating current and carry out waste liquid in the method for electrochemical rougheningization.(d) use the alternating current of 60Hz to carry out the electrochemical roughening processing continuously.Electrolyte in this processing is the aqueous solution of nitric acid (containing 0.5wt% aluminium ion and 0.007wt% ammonium ion) of the 1wt% under 40 ℃.AC power has shown that electric current is 2 milliseconds from the zero time T P that is increased to peak value, and duty factor is 1: 1, use trapezoidal shortwave alternating current, and uses carbon electrode as counter electrode: carry out the electrochemical roughening processing under these conditions.Use ferrite as auxiliary electrode.

Current density when current peak is 30A/dm ², the magnitude of current adds up to 250C/dm when aluminium plate is used as anode ²In impressed current anode, 5% current segment ground passes through from power supply.

Carry out the water flushing by spraying then.(e) being the NaOH of 2.6wt% and the aluminium ion etching aluminium plate that concentration is 6.5wt% by spraying concentration under 32 ℃ temperature, is 0.2g/m thereby make the meltage of aluminium plate ²The dirty component of mainly being made up of aluminium hydroxide that will produce in the time of will using alternating current to carry out electrochemical roughening in the above-mentioned stage is removed, and the marginal portion of the pit that produced is dissolved, thereby makes the marginal portion smooth.Carry out the water flushing by spraying then.(f) aqueous sulfuric acid (containing the 0.5wt% aluminium ion) by the 25wt% under spraying 60 ℃ goes not have optical processing, then, carries out the water flushing by spraying.(g) by using two known stepping material electrolysis mode anodization equipment of the front (length of the first time and the electrolysis section second time: respectively be 6m, the length of feeding part: 3m for the first time, the length of feeding part: 3m for the second time, for the first time and for the second time length of feed electrode: respectively be 2.4m) be that the sulfuric acid concentration (containing the 0.5wt% aluminium ion) of 170g/l and 38 ℃ temperature are carried out anodization with the electrolysis section.Then, carry out the water flushing through spraying.

In this step, in anodization equipment, be installed in the feed electrode first time on the feeding part for the first time from the current direction of power supply, the process electrolyte flow is to aluminium plate, the first time electrolysis section be on the surface of aluminium plate and form oxide film, and, get back to power supply by being installed in the electrolysis electrode on the feeding part first time.

On the other hand, be installed in the feed electrode second time on the feeding part for the second time from the current direction of power supply, and in the same manner, the process electrolyte flow is to aluminium plate, the second time electrolysis section be on the surface of aluminium plate and form oxide film, and be fed to for the first time from power supply that the magnitude of current of feeding part equates with the magnitude of current that is fed to the feeding part second time from power supply, and the second time feeding part the charging current density of oxide film be about 25 (D/dm ²).At the feeding part second time, be 1.35g/m by oxide film ²Surperficial inflow current.Final oxide film amount is 2.7g/m ²Stand to be called [A] up to the substrate of this phase process.

In substrate [A], the substrate of making through brush polishing step (a) is not called substrate [B].

In substrate [B], in anodization (g), be that 50 ℃ and charging current density are 5 (A/dm according to treatment temperature ²) the substrate of above-mentioned steps preparation be called substrate [C].

In substrate [B], in anodization (g), be that 10 ℃, charging current density are 40 (A/dm according to the treating fluid temperature ²) and sulfuric acid concentration be that the substrate of the above-mentioned steps preparation of 80g/l is called substrate [D].

In substrate [B], in anodization (g), be that 60 ℃, charging current density are 1 (A/dm according to the treating fluid temperature ²) and sulfuric acid concentration be that the substrate of the above-mentioned steps preparation of 350g/l is called substrate [E].

In substrate [B], be to soak the substrate in 10 seconds in 12 the sodium hydrate aqueous solution to be called substrate [F] at pH under 40 ℃.

In substrate [B], in anodization (g), be that 50 ℃, charging current density are 10 (A/dm according to the treating fluid temperature ²) and sulfuric acid concentration be that the substrate of the above-mentioned steps preparation of 300g/l is called substrate [G].

In substrate [B], in anodization (g), be that 5 ℃, charging current density are 50 (A/dm according to the treating fluid temperature ²) and sulfuric acid concentration be that the substrate of the above-mentioned steps preparation of 50g/l is called substrate [H].Image formation layer

At first, the fluid composition (sol solutions) for preparing the SG method according to following steps.Following composition is taken by weighing in the beaker, and stirred for 20 seconds down at 25 ℃.Si (OC ₂H ₅) ₄38g3-methacryloxypropyl trimethoxy silane 13g85% phosphate aqueous solution 12g ion exchange water 15g methyl alcohol 100g

This solution is transferred in the three-neck flask, be equipped with reflux condenser then and it is soaked at room temperature oil bath.In 30 minutes, the content in this three-neck flask is heated to 50 ℃ then, stirs with magnetic stirrer simultaneously.To bathe temperature simultaneously and remain on 50 ℃ of further reactions, to obtain fluid composition (sol solutions).With methyl alcohol/ethylene glycol=20/1 (weight ratio) this sol solutions is diluted to 20wt%, and it is applied on the substrate by gig, and following dry 1 minute at 100 ℃.Coating weight is 3.5mg/m ²About this coating weight, can also measure the Si amount of element according to fluorescent x-ary analysis, and with its as the coating value.

The photosensitive composition that will have following composition is applied on the aluminium plate of such processing, makes that dry back coating weight is 1.3g/m ² 80 ℃ of of following of and dry, 2 seconds, the following color compositions 2.0g methyl ethyl ketone 20g propane diols one ethyl ester 20g sensitizing pigment that forms of cyclopentadiene titanium compound 0.03g fluorine non-ionic surface active agent (F-177P) 0.03g thermal polymerization inhibitor (N-nitrosophenyl hydroxylamine aluminium salt) 0.01g of the following prescription of sensitizing pigment 0.07g of the following prescription of thereby form photographic layer. photosensitive composition tetramethylol methane tetraacrylate 1.5g benzyl methacrylate/methacrylic acid copolymer (copolymerization mol ratio=75/25) 2.0g

The cyclopentadiene titanium compound

Pigment P-18 (0.13 micron of the mean grain size of the following prescription of pigment dispensing composition, allyl methacrylate/methacrylic acid copolymer (copolymerization ratio 80/20, the weight-average molecular weight: 20g40000) cyclohexanone 35g acetate methoxyl propyl ester 115g pigment of the magnitude relationship of penetrability: 30g400nm＞500nm)

The preparation of protective seam

The aqueous solution (saponification degree 98mol%, the degree of polymerization 5500) of the polyvinyl alcohol (PVA) of 3wt% is coated on this photographic layer, makes that dried coating weight is 2g/m ², and 100 ℃ of following dry 2 seconds.

Being equipped with the galley presoma by the sensitization of using 400nm monochromatic light will obtain as mentioned above as light source exposes in the half tone image mode, control exposure power simultaneously, make that be 150 μ J with 175 row/inches from the version face exposure energy density of 10% spacing of 10-90%.Then, under 120 ℃, this version was heated for 20 seconds, to carry out the back heat treated.

By in the following developer solution under 25 ℃ this edition immersion being developed for 30 seconds.Developer solution 1K potassium silicate 30g potassium hydroxide 15gC ₁₂-H ₃₅-C ₆H ₄-O-C ₆H ₄-SO ₃Na 3g water 1000g

Then, water is with Fuji Photo Film Co., and the gummy liquid FP-2W that Ltd. produces is diluted to 2 times, and according to purposes the version surface is handled.With regard to the ability that stands duplicate printing, use Mitsubishi HeavyIndustries, the Dia 1F-2 that Ltd. produces is as printer, and use Dainippon Ink ﹠amp; Chemicals, the Graph G (N) that Inc. produces is as printing ink.Print with each 5000 sampling from printing beginning, and be printed to 150000 continuously.

Number when the printing ink concentration on the solid-state image part is begun to reduce is defined as the ability that stands duplicate printing.

Calculate the index of the printing Neutral colour % of Neutral colour part concentration according to Mary Devis formula as the runic Neutral colour.

The results are shown among the following table 4-2.

Table 4-2

	Substrate	The aperture	Hole density	Stand the ability of duplicate printing	With the color points area of 50% photographic fixing than (%)
						Embodiment 4-1	?A	?8nm	?1.1×10 16/m 2	100000	????70
Embodiment 4-2	?B	?8nm	?1.1×10 16/m 2	90000	????68
						Embodiment 4-3	?C	?6nm	?2.0×10 16/m 2	90000	????68
Embodiment 4-4	?D	?10nm	?9.0×10 15/m 2	110000	????75
						Comparative example 4-1	?E	?4nm	?4.0×10 15/m 2	70000	????85
Comparative example 4-2	?F	?13nm	?1.0×10 16/m 2	120000	????90
						Comparative example 4-3	?G	?5nm	?3.0×10 15/m 2	850000	????85
Comparative example 4-4	?H	?12nm	?7.0×10 15/m 2	105000	????84

On the SEM photo, use Hitachi, the scanning electron microscope S-900 that Ltd. produces observes not deposition of substrate surface, calculated hole diameters and hole density by the accelerating potential of 12kV with 150000 enlargement factor.The aperture is defined as the mean value of selecting 50 holes at random, and hole density is calculated by hole count in 600nm * 600nm.

As above show shown in the 4-2, under the situation of not destroying the ability that stands duplicate printing, increase by the aperture of anodic film and hole density being controlled at the point that constant scope can suppress to cause because of scattered light.

The oscillation wavelength that sensitive offset press version presoma of the present invention demonstrates cheap shortwave semiconductor laser has high sensitivity, and since aperture that will exist in the anodic film on the substrate and pore density be controlled in the given range and will contain optical property in the penetrability under the 500nm less than the photopolymerization layer of the pigment of the penetrability under 400nm as photographic layer, therefore can under bright safety light, operate.Because the tight contact between photographic layer and the substrate does not reduce, therefore sensitive offset press version presoma of the present invention has the good ability that stands duplicate printing.And because the runic color points that is formed by scattered light on substrate is not fragile, therefore sensitive offset press version presoma of the present invention has good color points repeatability.

Claims (7)

1. lithographic plate presoma comprises:

Through roughened and anodized aluminium substrate; With

Be provided at the photographic layer on the described substrate surface, said photographic layer contains infrared absorbing agents and water insoluble and be dissolved in the polymkeric substance of alkaline aqueous solution, and its solubleness in alkaline development solution changes because of infrared laser exposure;

Wherein said substrate obtains by the aluminium alloy version electrochemical rougheningization that will contain 0.05-0.5wt%Fe, 0.03-0.15wt%Si, 60-300ppmCu, 100-400ppm Ti and 10-200ppm Mg, contain at least a element in the column element under being selected from of 1-100ppm: Li, Na, K, Rb, Cs, Ca, Sr, Ba, Sc, Y, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Co, Rh, Ir, Pd, Pt, Ag, Au, C, Ge, P, As, S, Se, Te and Po, and aluminium purity is 99.0wt% or higher.

2. lithographic plate presoma as claimed in claim 1, wherein said substrate have following characteristics (a) and at least one characteristic (b):

(a) described substrate is 0.5 μ m or lower in the average roughness Ra of midline, and surface area is 2-30 per surface area doubly,

(b) have micropore in the described on-chip anodic film, its aperture is 1-5nm, and hole density is 8 * 10 ¹⁵-2 * 10/m ²

3. lithographic plate presoma as claimed in claim 1, vertical average surface roughness Ra of wherein said substrate reverse side is with laterally average surface roughness Ra is different, and suppose and to be expressed as Ral than the average surface roughness Ra on the big average surface roughness direction, and the average surface roughness Ra on the less average surface roughness direction is expressed as Ras, and then Ral and Ras satisfy the following relationship formula:

1.1≤Ral/Ras≤5.0。

4. lithographic plate presoma as claimed in claim 3, the reverse side of wherein said substrate carries out slight surface treatment, and handled zone is at least from the side of substrate reverse side one side, and width is more than or equal to 1mm and smaller or equal to 50mm.

5. lithographic plate presoma as claimed in claim 3, wherein when described photographic layer be to have when using in test cut tester (sapphire pin 0.5mm φ) and using the photographic layer on the abrasive surface of 30g load, on the substrate reverse side, form 0.1g/m ²Or more anodic film.

6. lithographic plate presoma as claimed in claim 4, wherein when described photographic layer be to have when using in test cut tester (sapphire pin 0.5mm φ) and using the photographic layer on the abrasive surface of 30g load, on the substrate reverse side, form 0.1g/m ²Or more anodic film.

7. lithographic plate presoma as claimed in claim 1, wherein the aperture of the micropore that exists in described on-chip anodic film is 1-5nm, and hole density is 8 * 10 ¹⁵-2 * 10 ¹⁶/ m ², and described photographic layer contains

(ⅰ) at least a cyclopentadiene titanium compound,

But (ⅱ) have at least one alkene formula unsaturated double-bond addition polymerization compound and

(ⅲ) at least a pigment with optical property that penetrability is littler than penetrability under the 400nm under the 500nm.

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