CN1228189C - Original plate of lithographic plate - Google Patents

Abstract

The invention provides a heat sensitive presensitized plate, which comprises a support for a lithographic printing plate including an anodized layer formed on an aluminum plate and a recording layer recordable by infrared laser exposure on the support, wherein in a section of the anodized layer after the recording layer is provided, an atomicity ratio of carbon to aluminum (C/Al) represented by Auger Electron Spectroscopic analysis is 1.0 or less. In the case of being used as an on-machine development type, it exhibits a good on-machine development characteristic, a high sensitivity, a high press life, and high scum resistance during printing and while left (ink discharging). In the case of being used as a conventional thermal positive or negative working type, it exhibits an efficient use of heat for image formation, a high sensitivity, a high press life, and a slight possibility of scum occurrence at non-image areas.

Description

Lithographic printing original and manufacture method thereof

Technical field

The present invention relates to supporter and original edition of lithographic printing plate that a kind of lithographic plate adopts, in more detail, the present invention relates to a kind of sensible heat type original edition of lithographic printing plate that is applicable to CTP (the computer to plate) system that need not to develop, promptly, can be according to data signal by noctovisor scan exposure carrying out image record, after the exposure, need not through original developing procedure, the sensible heat type original edition of lithographic printing plate that the existing printing machine of can packing into prints and the lithographic plate supporters of employing thereof such as use developer solutions.

Background technology

Original edition of lithographic printing plate for the significant CTP of development in recent years system is adopted has carried out a lot of researchs.Wherein, rationalize and the liquid waste processing problem in order further to solve engineering, the original edition of lithographic printing plate that can print the existing printing machine of packing into after the exposure has carried out a lot of researchs, and has proposed various motions.

A promising technology proposes a kind of sensible heat type original edition of lithographic printing plate, and the hydrophilic layer that it forms so that hydrophobic thermoplasticity polymer particle is dispersed in the hydrophilic adhesive polymer is as the imaging heat sensing layer.In a single day this original edition of lithographic printing plate utilization heats this heat sensing layer, and hydrophobic thermoplasticity polymer particle can melt, and is the principle of oil loving image portion thereby make hydrophilic heat sensing layer surface conversion.

As a way that reduces treatment process, pack into original edition of lithographic printing plate after the exposure of the original edition of lithographic printing plate that the heat of such polymer particle that utilizes the hydrophobicity thermoplasticity is melted need not on the cylinder of the printing machine handled with developer solution, in the head roll rotation, by supplying with printing ink and/or dumping processing solution, can remove the non-image part in the original edition of lithographic printing plate, this is a kind of method of developing on the machine that is called as.This method is after original edition of lithographic printing plate exposure, in its existing printing machine of packing into, finishes development treatment in common printing process process.

Be applicable to that the original edition of lithographic printing plate that develops on the above-mentioned machine will have the heat sensing layer that dissolves in dumping processing solution and the printing ink solvent, and the bright chamber property handled must be arranged, promptly be suitable for the characteristic that is developed on the printing machine of bright chamber placing.

For example, put down in writing a kind of original edition of lithographic printing plate in the specification that No. the 2938397th, the Japanese Patent Laid communique, it be provided with on the hydrophily supporter one deck with the microparticulate of thermoplasticity hydrophobic polymer in hydrophilic binder polymer and the heat sensing layer that forms.Put down in writing in this patent specification aforementioned original edition of lithographic printing plate after exposure under the infrared laser, the combination under the effect of heat of the particulate of the hydrophobic polymer of thermoplasticity, form after the image, galley is installed on the cylinder of printing machine, supplies with printing ink and/or dumping processing solution and can develop on the realization machine.

And also put down in writing in the Japan Patent open flat 9-127683 of communique number and No. 99/10186 book of PCT communique, the thermoplasticity particulate under the effect of heat in conjunction with after, can be made into lithographic plate by developing on the machine.

But, the heat of passing through although it is so makes particulate show the characteristic of developing on the good machine in conjunction with the original edition of lithographic printing plate that forms image, but also exist because heat is loose on metal support, the problem that the speed that causes reduces and when particulate when insufficient, the weakened of the image portion of heat sensing layer causes problems such as anti-seal is not enough.

As countermeasure, proposed between aluminium support body and heat sensing layer, to be provided with the method (for example, open communique 2000-23983 number of Japan Patent) of water-fast organic polymer, though speed has improved, but there is the problem of spot.

Thus, the infrared absorbent that is present in the heat sensing layer is brought into play its photo-thermal transformation, generate heat by exposure, the exposed portion of heat sensing layer becomes alkaline soluble by this heat, thereby the original edition of lithographic printing plate of the so-called sensible heat type positive type of formation erect image and free radical generating agent and acid-producing agent generate free radical and acid by this heat, and formation Raolical polymerizable and sour cross-linking reaction, thereby can't dissolve, thereby the original sensible heat type original edition of lithographic printing plate that does not carry out developing on the machine of the sensible heat type negative-type original edition of lithographic printing plate of formation negative-appearing image type image etc. all has following shortcoming.

Promptly, above-mentioned such sensible heat type imaging is to shine by laser, photo-thermal conversion material produces heat in heat sensing layer, cause what imaging was reacted by this heat, but owing to forming at surface coarsening in the aluminium support body of anode oxide film, the thermal conductivity ratio heat sensing layer of supporter is much higher, and therefore the heat of the generation of the near interface between heat sensing layer and supporter can not fully make land used to the supporter diffusion inside for imaging, and its result will cause phenomenon as described below on the supporter interface of heat sensing layer.

At first, in the heat sensing layer of positive type, if hot diffusion inside to supporter, then alkaline bleach liquor soluble reaction can react insufficient, thereby produces residual film on non-image part originally, forms the problem of low speed, and this is the essential problem of positive type heat sensing layer.

And, such sensible heat type positive type original edition of lithographic printing plate must contain the infrared absorbent with photo-thermal translation function, but because the molecular weight ratio of absorbent is bigger, therefore dissolubility is also just lower, and absorbent all is adsorbed on the minute opening portion place that is formed by anodic oxidation, therefore is difficult to remove, in the operation of developing, exist the problem that is easy to generate residual film with alkaline-based developer.

On the other hand, in the heat sensing layer of negative-type, if heat is to the supporter diffusion inside, then the immobilization of the developer solution of the heat sensing layer at the supporter near interface place of heat sensing layer will become insufficient, the part place that therefore should form image portion originally can not be completed into image, cause or also can flow when developing, or promptly enable to form the complexion of image, image also is easy to the problem peeled off during printing.

Address the above problem, the heat that produces from suppress heat sensing layer has carried out enlarging the trial of the micropore of anode oxide film to the angle of aluminium support body diffusion.

But the method that enlarges the micropore of anode oxide film has improved speed and Nai Yin, however but deterioration of spot-resistant.And, on machine is set during the heat sensing layer of developable, also deterioration of development on the machine.

Subsequently, from same viewpoint, form aluminium support body by anode oxide film is set on aluminium sheet, and this aluminium support body immersed hot water and inorganic salts or contain the method in the hydrothermal solution of organic salt and be exposed to the method for steam in bathing etc., carried out the trial of closed porosity.

But though the method for closed porosity has improved spot-resistant, speed and Nai Yin be deterioration but.And above-mentioned which kind of trial all can not reach satisfied fully level.

To this, the inventor is in the specification of Japanese Patent Application Publication communique 2001-9871 number, proposed a kind of original edition of lithographic printing plate, being provided with by average grain diameter successively by following order on the aluminium support body that this printing plate precursor is made on the aluminium sheet anode oxide film being set is the particle layer that constitutes of the particle of 8～800nm and the recording layer that can write by the infrared laser exposure.And having proposed to contain average grain diameter by employing in aforementioned specification is that the electrolyte of the hydrophilic particles of 8～800nm comes the aforementioned aluminium support body of electrolytic treatments, thereby the method for aforementioned particles layer is set on aforementioned aluminium support body.Adopt this method, both can reserve hole, block its opening, obtain ISO, the good original edition of lithographic printing plate of anti-seal, but also can improve spot-resistant in the micropore inside that is positioned on the anode oxide film.

But the said spot-resistant that improved not is to have reached optimal degree.

Summary of the invention

First purpose of the present invention provides a kind of sensible heat type original edition of lithographic printing plate of the shortcoming that has overcome above-mentioned prior art and the used supporter of lithographic plate that is applicable to this master.Be that first purpose of the present invention is the used supporter of lithographic plate that a kind of original edition of lithographic printing plate of sensible heat type is provided and is applicable to this master, when as on the machine during developable, it has developing performance on the good machine, the speed height, show Gao Naiyin, and being difficult to during printing forms spot and set-off (adhering to printing ink) is good, when as existing sensible heat type positive type and sensible heat type negative-type, it can efficiently utilize heat in imaging process, the speed height, show Gao Naiyin, and non-image part is difficult to form spot.

In addition, second purpose of the present invention provides a kind of manufacture method of original edition of lithographic printing plate, and it can efficiently utilize heat in imaging process, and speed height, anti-seal are good, and anti-formation spot is good.

" in order to solve the means of problem "

The inventor is in order to reach above-mentioned first purpose, through discovering, anodic oxidation coating is provided with by infrared laser exposes in the original edition of lithographic printing plate of writeable recording layer, the composition of recording layer is invaded in the micropore of anodic oxidation coating, because this recording layer composition is than the pyroconductivity height of the hole portion (micropore) of anodic oxidation coating, the pyroconductivity that anodic oxidation coating behind the recording layer therefore is set increases, and can produce the problems referred to above.The inventor is according to above-mentioned discovery, further research, if the carbon component in the discovery anodic oxidation coating and the ratio of aluminium component are below particular value, anti-seal, speed and the anti-scumming that will obtain lithographic printing-plate be original edition of lithographic printing plate preferably all, and finishes first scheme of the present invention thus.

Promptly, the invention provides a kind of lithographic printing-plate that constitutes forming anodic oxidation coating on the aluminium sheet with supporter on, setting is by the infrared laser original edition of lithographic printing plate that writeable recording layer forms that exposes, be provided with in the cutting plane of this anodic oxidation coating behind this recording layer, by the atomicity of the carbon of following formula (1) expression and aluminium than (C/Al) below 1.0:

C/Al＝(I _C/S _C)/(I _al/S _al)

I _C: the auger electrons derivative-type peak of carbon (KLL) is to peak intensity

I _AlThe auger electrons derivative-type peak of aluminium (KLL) is to peak intensity

S _C: the relative sensitivity coefficient of the auger electrons of carbon (KLL)

S _AlThe relative sensitivity coefficient of the auger electrons of aluminium (KLL)

The porosity that aforementioned recording layer aforesaid anode oxide film thereon before is set is preferably 20～70%.

The porosity that anodic oxidation coating before the aforementioned recording layer is set is 20～70%, and the diameter of micropore that exposes the surface of this anodic oxidation coating is preferably in below the 15nm.

Decide the anodic oxidation coating of porosity on the aluminium support body surface by forming, can reduce the heat conductivity at heat sensing layer supporter interface, improve speed and Nai Yin at the inner thermal insulation layer that has a plurality of hole parts that forms of this anodic oxidation coating.

And, the diameter of the micropore by will exposing the anodic oxidation coating surface (below be called " surface apertures ") is controlled under the specific numerical value, can keep the effect that improves speed and Nai Yin, and the effect of development and anti-set-off on can the reduction machine.Can prevent effectively like this because the problems such as residual film that the lipophilic constituent of the dyestuff, adhesive in the recording layer etc. causes, and owing to improved hydrophily, therefore anti-scumming is also better.

The porosity of fixed anodic oxidation coating and surface apertures in order to obtain for example can be enumerated the method with acid or alkali treatment anodic oxidation coating surface.Also can handle combined with sealing of hole.

Aforementioned recording layer preferably contains

(a) have heat reactivity functional group's particulate polymer, or

(b) inside comprises the heat sensing layer of the microcapsules of the compound with heat reactivity functional group.

The inventor is in order to solve above-mentioned second purpose, the result of research proposes in Japanese patent application 2001-9871 specification, set gradually on the aluminium support body that forms on the aluminium sheet anodic oxidation coating being set by average grain diameter be the particle layer that constitutes of the particle of 8～800nm, and by the infrared laser writeable recording layer that exposes, in such original edition of lithographic printing plate, by soaking or coating formation particle layer, can suppress non-image part more and produce the scumming phenomenon, thereby finish alternative plan of the present invention.

Promptly, the invention provides a kind of manufacture method of original edition of lithographic printing plate, the aluminium support body that aluminium sheet is provided with anodic oxidation coating and forms is immersed in and contains in the liquid of hydrophilic particles that average grain diameter is 8～800nm, on this aluminium support body, form particle layer, and will be arranged on this particle layer, thereby obtain original edition of lithographic printing plate by the infrared laser writeable recording layer that exposes.The present invention also provides a kind of original edition of lithographic printing plate, set gradually on the aluminium support body that forms being provided with anodic oxidation coating on the aluminium sheet by average grain diameter be the particle layer that constitutes of the particle of 8～800nm, and by the infrared laser writeable recording layer that exposes, thereby the original edition of lithographic printing plate that obtains according to aforementioned manufacture method.

The invention provides a kind of manufacture method of original edition of lithographic printing plate, coating contains the liquid that average grain diameter is the hydrophilic particles of 8～800nm on the aluminium support body that forms being provided with anodic oxidation coating on the aluminium sheet, on this aluminium support body, form particle layer, and will be arranged on this particle layer, thereby obtain original edition of lithographic printing plate by the infrared laser writeable recording layer that exposes.The present invention also provides a kind of original edition of lithographic printing plate, set gradually on the aluminium support body that forms being provided with anodic oxidation coating on the aluminium sheet by average grain diameter be the particle layer that constitutes of the particle of 8～800nm, and by the infrared laser writeable recording layer that exposes, thereby the original edition of lithographic printing plate that obtains according to aforementioned manufacture method.

In the manufacture method of above-mentioned original edition of lithographic printing plate, after particle layer is set, before forming heat sensing layer, preferably carry out hydrophilicity-imparting treatment.

The pyroconductivity of aforementioned hydrophilic particles is preferably in below the 60W/ (mK).

The present invention also provides the original edition of lithographic printing plate of the present invention's first scheme that a kind of manufacture method of original edition of lithographic printing plate of the alternative plan according to the invention described above obtains.

Fig. 4 is the cutting plane ideograph of the original edition of lithographic printing plate that obtains according to alternative plan of the present invention.As shown in Figure 4, on the aluminium support body 4 that the original edition of lithographic printing plate 1 that obtains according to alternative plan of the present invention constitutes being provided with anodic oxidation coating 3 on the aluminium sheet 2, have the particle layer 5 that constitutes by the hydrophilic particles of 8～800nm by average grain diameter, and fixed heat sensing layer 6 successively.Micropore 7 on the anodic oxidation coating 3 has been stopped up by particle layer 5, but inside still has hole.During existing sealing of hole was handled, the micropore on the anodic oxidation coating had been lived by fillings such as boehmites, does not almost have hole, and this and micropore of the present invention inside have the hole this point to differ greatly.

The original edition of lithographic printing plate that obtains according to the present invention passes through to adopt said structure, owing to can have the effect of heat insulation that the hole of effect of heat insulation that particle layer brings and micropore brings simultaneously, therefore can fully suppress to utilize the thermosetting image more expeditiously from the thermal diffusion of heat sensing layer to aluminium support body.

Thus, can obtain the good original edition of lithographic printing plate of particularly anti-scumming by soaking or applying the formation particle layer.

And, according to the present invention, can finish the speed height, anti-seal is good and non-image part more is difficult to the original edition of lithographic printing plate of scumming.

And then, the invention provides a kind of plate-making and printing process of lithographic printing-plate, the original edition of lithographic printing plate of the invention described above can be carried out image exposure by laser after, be installed on the printing machine and print, carry out image exposure with laser after perhaps on being installed to printing machine, print again.

Description of drawings

Fig. 1 is the example that the cutting plane for the anodic oxidation coating of original edition of lithographic printing plate carries out the chart that the auger electrons spectrum analysis obtains.

Fig. 2 is the oscillogram that expression is applicable to an example of trapezoidal wave used in the electrochemical surface coarsening processing of employing alternating current of the present invention.

Fig. 3 is the side view that expression is applicable to an example of the radial mode electrolytic cell in the electrochemical surface coarsening processing of the present invention.

Fig. 4 is the generalized section of the original edition of lithographic printing plate that obtains according to alternative plan of the present invention.

Fig. 5 is the electron micrograph of section of an example of the original edition of lithographic printing plate that obtains according to alternative plan of the present invention.

[explanation of symbol]

1 original edition of lithographic printing plate

2 aluminium sheets

3 anodic oxidation coating

4 aluminium support bodies

5 particle layers

6 heat sensing layers

7 micropores

The surface of 8 non-image parts

11 aluminium sheets

12 cylinders radially

13a, 13b main pole

14 acidic aqueous solutions

15 solution supply ports

16 narrow slits

17 solution paths

18 impressed current anodes

19a, 19b thyratron transistor

20 AC powers

21 main electrolytic cells

22 impressed current anode grooves

The specific embodiment

＜aluminium sheet (aluminum) 〉

As the aluminium sheet of original edition of lithographic printing plate of the present invention is to be the metal of main component by the aluminium with the profile dimensionally stable, and promptly aluminum or aluminum alloy is made.Except pure aluminum plate, can also adopt with aluminium is alloy sheets, lamination aluminum or aluminum alloy or the evaporation aluminum or aluminum alloy plastic sheet or the scraps of paper that form that contain other element of trace of main component.And then, can also adopt as putting down in writing on the clear 48-18327 communique of Japanese Patent Application Publication, on pet film in conjunction with the aluminium thin layer form compound for the one thin layer.

There is no particular limitation for aluminium sheet of the present invention, but it is only adopting pure aluminum plate.Because pure fully aluminium is technical in refining to be to be difficult to make, therefore adopting a little, the aluminium sheet of a little other elements of band also is fine.Suitably adopt aluminium handbook for example the 4th edition (light metal association (1990)) to go up well known materials of record, specifically, for example JIS A1050, JIS A1100, JIS A3005, the aluminium alloy plate of international registration alloy 3103A etc. all is fine.In addition, also can to use the content of aluminium (Al) be 99.4～95wt% and contain the aluminium alloy more than at least 5 kinds, the aluminium scrap material in iron (Fe), silicon (Si), copper (Cu), magnesium (Mg), manganese (Mn), zinc (Zn), chromium (Cr) and the titanium (Ti) or use the aluminium sheet of the secondary pig iron in the aftermentioned scope.

Among the present invention, in order to reduce cost, the content that can also use Al is the aluminium sheet of 95～99.4wt%.When the content of Al surpasses 99.4wt%,, can cause cost to rise because the allowance of impurity has reduced.And when the discontented 95wt% of the content of Al, the content of impurity increases, and can cause occurring in rolling problems such as crackle.Situation is that the content of Al is 95～99wt% preferably, preferably at 95～97wt%.

The content of Fe is preferably 0.1～1.0wt%.Even Fe is the element that also contains in the new pig iron about 0.1～0.2wt%, the amount of solid solution has reduced in Al, and is nearly all remaining as intermetallic compound.If the content of Fe surpasses 1.0wt%, just in the operation of rolling, crack easily, if discontented 0.1wt% then can not reduce cost.Situation is that the content of Fe is 0.3～1.0wt% preferably.

The content of Si is 0.03～1.0wt% preferably.Si is the higher element of content in the chip of JIS2000 series, 4000 series, 6000 series materials.Even and Si is the element that also contains in the new pig iron about 0.03～0.1wt%, it is the state of solid solution in Al, perhaps exist as intermetallic compound.If to the aluminium sheet heating, the Si of solid solution becomes monomer Si and separates out in the manufacture process of supporter.As everyone knows, the intermetallic compound of monomer Si and FeSi system has very bad influence to the printing ink spot of anti-harshness.At this, so-called " harsh printing ink spot " is meant and has no progeny in the printing several times when carrying out again, adheres to printing ink easily on the non-image part surface of plate printing plate, point-like or circular spot occur on the surfaces such as paper behind its result's seal.In case the content of Si surpasses 1.0wt%, for example, aftermentioned is with possibly removing fully in the sulfuric acid treatment (going spot to handle), if but less than 0.15wt%, then can weaken the effect that reduces cost.Preferably the content of Si is 0.05～1.0wt%.

The content of Cu better is 0.000～1.0wt%, preferably 0.000～0.3wt%.Cu is the higher element of content in the material chip of JIS2000 series, 4000 series.The Cu ratio is easier to solid solution in Al.If the content of Cu surpasses 1.0wt%, for example handle or go and possibly can't remove fully in the spot processing at sour corrosion described later.Herein, the content of Cu is 0.000wt%, and 0.000 order of magnitude can't detect, and content is that 0wt% is the trace that expression can't be explained.Below, the lower limit of content is designated as 0.000wt% and means the same meaning.

The content of Mg is preferably 0.000～1.5wt%.Mg is the more element of content in the chip of JIS2000 series, 3000 series, 5000 series, 7000 series materials.Particularly content is more in the can end material, is one of main impure metal that comprises in the chipped material therefore.Mg also than being easier to be solid-solubilized among the Al, forms intermetallic compound with Si.In case the content of Mg surpasses 1.5wt%, for example in sulfuric acid treatment described later, just possibly can't remove fully.

The content of Mn is preferably 0.000～1.5wt%.Mn is the more element of content in the chip of JIS3000 series material.Mn particularly in can body material content more, therefore be one of main impure metal that comprises in the chipped material.The Mn ratio is easier to be solid-solubilized among the Al, forms intermetallic compound with Al, Fe and Si.In case the content of Mn surpasses 1.5wt%, for example in sulfuric acid treatment described later, just possibly can't remove fully.

The content of Zn is preferably 0.000～0.5wt%.Zn is the more element of content in the chip of JIS7000 series particularly.The Zn ratio is easier to be solid-solubilized among the Al.In case the content of Zn surpasses 0.5wt%, for example in sulfuric acid treatment described later, just possibly can't remove fully.

The content of Cr is preferably 0.000～0.1wt%.Cr is the less impure metal of content in the chip of JIS A5000 series, 6000 series, 7000 series.In case the content of Cr surpasses 0.1wt%, for example in sulfuric acid treatment described later, just possibly can't remove fully.

The content of Ti is preferably 0.003～0.5wt%.Ti is the element that adds 0.01～0.04wt% as common crystallization miniaturization material.More as impure metal content in the chip of JIS5000 series, 6000 series, 7000 series.In case the content of Ti surpasses 0.5wt%, for example in sulfuric acid treatment described later, just possibly can't remove fully.

The aluminium sheet that the present invention adopts is cast out by usual method with above-mentioned raw material, and through suitable rolling processing and heat treatment, thickness is for example 0.1～0.7mm, and necessary words can also be carried out flatness and be proofreaied and correct processing.Its thickness can suitably change according to the size of printing machine, the size of galley and user's needs.

In addition, the manufacture method of above-mentioned aluminium sheet can adopt DC casting for example, omits equal heat treatment and/or burn the method and the continuous metal cast process of blunt processing from the DC casting.

The aluminium support body that offset printing plate originals of the present invention is adopted carries out anodized to above-mentioned aluminium sheet and obtains, but also can comprise the various operations except that anodized in its manufacturing process.

Above-mentioned aluminium sheet is preferably handled, is covered the anodized operation of surface of aluminum plate with oxide film thereon through the surface coarsening that goes the spot treatment process, surface of aluminum plate is carried out alligatoring of the spot of the degreasing process of the ROLLING OIL of removing attachment removal, dissolving surface of aluminum plate, forms supporter.

The manufacturing process of aluminium sheet supporter of the present invention preferably is included in and adopts alternating current in the acidic aqueous solution, aluminium sheet is carried out the surface coarsening of electrochemistry alligatoring and handles (electrochemical surface coarsening processing).

And, preferably also comprise the surface treatment procedure of the aluminium sheet of the combined machine roughening treatment except that above-mentioned electrochemical surface roughening treatment, the chemical attack processing in acid or aqueous alkali etc. in the manufacturing process of the aluminium sheet supporter that the present invention adopts.The manufacturing process of the surface coarsening processing of the aluminium sheet supporter that the present invention adopts etc. can be that continuity method also can be a hit and miss method, but preferably adopts continuity method on the operation.

And then among the present invention, processing, the sealing of hole that if necessary, can also carry out acid treatment or alkali treatment, carries out with the aqueous solution that contains inorganic fluorine compounds and silicate compound handled, hydrophilic surface is handled.And then, if necessary, also priming coat can be set.

Particularly, as described later, can immerse and contain in the liquid of hydrophilic particles that average grain diameter is 8～800nm aluminium support body that anodic oxidation coating forms is set on aluminium sheet, on this aluminium support body, form particle layer, perhaps also can on this aluminium support body, apply and contain the liquid that average grain diameter is the hydrophilic particles of 8～800nm, thereby on this aluminium support body, form particle layer.

＜surface coarsening is handled (graining processing) 〉

At first, surperficial roughening treatment is described.

Above-mentioned aluminium sheet will carry out graining and handle in order to have better shape.The graining that the method that graining is handled has the spy to drive the machinery of clear 56-28893 communique record is handled the surface coarsening of (roughening treatment of machinery), chemical attack, electrolysis etc.And then, can also adopt in electrolysis of hydrochloric acid liquid or carry out in the nitric acid electrolyte electrochemistry graining facture (electrochemical roughening treatment, electrolyzing and coarsening are handled) that electrochemical graining handles, slightly legal with the wire on wire scratching aluminium surface, form the mill ball roughening method of graining on the aluminium surface, form the mechanical roughening method (surface coarsening of machinery is handled) of the brush roughening method etc. of graining with nylon bruss and grinding agent on the surface with mill ball and grinding agent.These graining methods can be used alone or in combination.For example, can adopt the combination that the electrolyzing and coarsening of the mechanical roughening treatment of nylon bruss and grinding agent and electrolysis of hydrochloric acid liquid or nitric acid electrolyte handles, the combination of repeatedly electrolytic surface roughening treatment etc.Wherein, electrochemical surface coarsening is handled better.Surface coarsening that also can combined machine is handled and electrochemical roughening treatment, and it is best particularly carrying out electrochemical roughening treatment again after the surface coarsening processing of carrying out machinery.

The surface coarsening of machinery is handled and to be to use brush etc. to carry out the roughening treatment of machinery in surface of aluminum plate, carries out before being preferably in electrochemical roughening treatment.

In the suitable mechanical surface roughening treatment, adopting the hair footpath is that the rotation nylon brush roll of 0.07～0.57mm and the slurries of supplying with the grinding agent of surface of aluminum plate are handled.

The water imbibition of nylon bruss is low more good more, for example, the nylon bristles brush 200T (6 that Dong She makes, 10-nylon, softening point: 180 ℃, fusing point: 212～214 ℃, proportion: 1.08～1.09, water content: be 1.4～1.8 under the situation of 20 ℃ of relative humidity 65%, be 2.2～2.8 under the situation of 20 ℃ of relative humidity 100%, dry hot strength: 4.5～6g/d, dry degree of drawing: 20～35%, the shrinkage factor of boiled water: 1～4%, Gan Zao tensile resistance degree: 39～45g/d, Young's modulus (drying): 380～440kg/mm ²).

As grinding agent, can adopt known product, but preferably adopt special silica sand, quartz, aluminium hydroxide or these the mixture of putting down in writing in flat 6-135175 communique and the special public clear 50-40047 communique of opening.

As slurries, its proportion is preferably in 1.05～1.3 the scope.As the method for slurries being supplied with surface of aluminum plate, can adopt the method that for example sprays slurries, with the method for metal plug, will be transferred to method on the aluminium sheet etc. with the surface configuration of concavo-convex Rolling roller.Also can adopt the spy to open the method for putting down in writing in clear 55-074898 communique, 61-162351 communique, the 63-104889 communique.And then, as the spy shows to put down in writing in the flat 9-509108 communique, the water-soluble serous Ginding process of brushing in surface of aluminum plate that can adopt the mixture by aluminium oxide and the quartzy particle that constitutes 95: 5～5: 95 weight ratio scope in, to form.The average grain diameter of the said mixture of this moment is 1～40 μ m, preferably in the scope of 10～30 μ m.

Electrochemical roughening treatment is in acidic aqueous solution, feeds alternating current with aluminium sheet as electrode, electrochemical surface coarsening is carried out on the surface of this aluminium sheet handle, and is different with above-mentioned mechanical surface roughening treatment.If adopt electrochemical surface coarsening to handle,, therefore can suitably improve the adherence between heat sensing layer and the supporter owing to be easy to form from the teeth outwards trickle concavo-convex.

Among the present invention, during above-mentioned electrochemical surface coarsening is handled, the electric weight of aluminium sheet during, the electric weight when promptly electric weight Qc and aluminium sheet are as anode during negative electrode, i.e. electric weight Q during anode as negative electrode _ARatio Qc/Q _AIn 0.5～2.0 scope for example, therefore can on the surface of aluminium sheet, generate the cellular hole of homogeneous.If Qc/Q _ABe discontented with 0.5, the inhomogenous cellular hole of then easy generation, but surpass 2.0, the inhomogenous cellular hole of also easy generation.Qc/Q _ABe preferably in 0.8～1.5 the scope.

Waveform as the alternating current that adopts in the electrochemical surface coarsening processing can adopt sine wave (sin ripple), square wave, triangular wave, trapezoidal wave etc.Wherein preferably adopt square wave or trapezoidal wave.And the frequency of alternating current better is 30～200Hz from the angle of the cost of manufacture of supply unit, preferably 40～120Hz.

An example of the trapezoidal wave that the present invention is suitable for as shown in Figure 2.Among Fig. 2, the longitudinal axis is represented current value, and transverse axis is represented the time.Ta represents the reaction time of anode, tc represents the reaction time of negative electrode, tp represents that current value is from 0 time till the peak value of negative electrode cycle side, tp ' expression current value is from 0 time till the peak value of anode cycle side, electric current when the electric current when Ia represents the peak value of anode cycle side, Ic are represented the peak value of negative electrode cycle side.When the waveform of alternating current adopts trapezoidal wave, electric current from 0 to the time tp of peaking and tp ' preferably respectively in the scope of 0.1～2msec, be preferably in the scope of 0.3～1.5msec.Tp and tp ' are if discontented 0.1msec then can influence the impedance in the electric power loop, and current waveform must have big supply voltage when rising, and can improve the cost of power-supply device.And if tp and tp ' surpass 2msec, then can increase influence to micro constitutent in the acidic aqueous solution, cause being difficult to carry out the surface coarsening processing of homogeneous.

Consider that from the angle of surface of aluminum plate homogeneous alligatoring the power of the alternating current that adopts during electrochemical surface coarsening is handled is more fortunately in 0.25～0.5 the scope, be preferably in 0.3～0.4 the scope." power (duty) " of the present invention is meant in the period T of alternating current, and the time that the anode reaction of aluminium sheet is lasting, this power was ta/T when being made as ta.Particularly, on surface of aluminum plate during anode reaction except generating spot composition based on aluminium hydroxide, also can produce the dissolving and the destruction of oxide film thereon, because after this anode reaction of aluminium sheet becomes the starting point of pit corrosion reaction constantly, so the selection of the power of alternating current is very big to the influence that the uniform surface alligatoring produces.

The current density of alternating current is when trapezoidal wave or square wave, and the current density Icp when current density Iap during anode cycle side peak value and negative electrode cycle side peak value is preferably respectively at 10～200A/dm ²Scope in, better at 10～100A/dm ²Scope in.And Icp/Iap is preferably in 0.9～1.5 the scope.

In electrochemical surface coarsening was handled, the summation of the employed electric weight of anode reaction that electrochemical surface coarsening is handled the aluminium sheet of the finish time was 50～1000C/dm preferably ², be 50～800C/dm better ², be preferably 50～400C/dm ²The time that electrochemical surface coarsening is handled is preferably 1 second～and 30 minutes.

As the acidic aqueous solution that adopts in the electrochemical surface roughening treatment, can adopt the solution of using in the electrochemical surface roughening treatment of common use direct current or alternating current, wherein preferably adopt based on the acidic aqueous solution of nitric acid or based on the acidic aqueous solution of hydrochloric acid.Herein, " for main body " is meant that the composition as main body accounts for 30wt% with respect to whole compositions in the aqueous solution, preferably accounts for more than the 50wt%.It also is same regarding to other composition down.

Based on the acidic aqueous solution of nitric acid as mentioned above, can adopt the solution of using in the electrochemical surface roughening treatment of common use direct current or alternating current.For example, can be with in the nitrate compound of aluminum nitrate, sodium nitrate, ammonium nitrate etc. one or more, add to the aqueous solution of nitric acid that concentration of nitric acid is 5～15g/L and use to reach saturated concentration from 0.01g/L.In acidic aqueous solution, also can be dissolved with the metal that comprises in the aluminium alloy of iron, copper, manganese, nickel, titanium, magnesium, silicon etc. based on nitric acid.

Can adopt based on the acidic aqueous solution of nitric acid and wherein to contain nitric acid, aluminium salt, nitrate, and at aluminium ion is 1～15g/L, be preferably 1～10g/L, ammonium ion is under the situation of 10～300ppm, is to add aluminum nitrate and the resulting solution of ammonium nitrate in the aqueous solution of nitric acid of 5～15g/L at concentration of nitric acid.Above-mentioned aluminium ion and ammonium ion produce in carrying out electrochemical surface coarsening processing procedure naturally, increase gradually.The fluid temperature of this moment is preferably 10～95 ℃, more preferably 20～90 ℃, is preferably 40～80 ℃.

When the acidic aqueous solution that adopts based on hydrochloric acid,, just can form trickle concavo-convex from the teeth outwards as long as therefore apply seldom electrolysis because hydrochloric acid self is strong to the dissolving power of aluminium.This trickle concavo-convex average opening diameter is 0.01～0.2 μ m, the generation of homogeneous on the whole surface of aluminium sheet.In order to obtain such graining, the summation of the electric weight that anode reaction stood of the aluminium sheet of cell reaction finish time is preferably 1～100C/dm ², be preferably 20～70C/dm ²The current density of this moment is preferably 20～50A/dm ²

In the electrochemical surface roughening treatment that employing is carried out based on the electrolyte of hydrochloric acid, the summation of the electric weight that is stood in the anode reaction increases to 400～1000C/dm ², therefore may form crateriform big ripple simultaneously, the crateriform ripple that this moment, average opening diameter was 10～30 μ m is overlapping, and forming average opening diameter on whole surface is the trickle concavo-convex of 0.01～0.4 μ m.

When adopting the electrolyte of above-mentioned nitric acid, hydrochloric acid etc. to carry out repeatedly electrolytic surface roughening treatment, be preferably in and carry out catholyte on the aluminium sheet and handle.Handle by this catholyte, on surface of aluminum plate, generate in the spot,, therefore can carry out the electrolytic surface roughening treatment more equably owing to produced hydrogen.Cathode capacity in the acid solution that this catholyte is handled is preferably 3～80C/dm ², be preferably 5～30C/dm ²If cathode capacity is less than 3C/dm ², the adhesion amount deficiency of spot then is if but surpass 80C/dm ², then the adhesion amount of spot is excessive, and which kind of situation is all bad.In addition, electrolyte can be identical with the solution that uses in the above-mentioned electrolytic surface roughening treatment, also can be different.

In electrochemical surface coarsening is handled, can use known electrolysis units such as longitudinal type, flat pattern, radial mode, good especially but the spy drives the radial mode electrolysis unit of putting down in writing in the flat 5-195300 communique.

Fig. 3 is the skeleton diagram that is applicable to radial mode electrolysis unit of the present invention.Among Fig. 3, in the electrolysis unit of radial mode, aluminium sheet 11 is wound on the radially roller 12 that is arranged in main electrolytic cell 21, carries out electrolytic treatments by main pole 13a that links to each other with AC power 20 and 13b in course of conveying.Acidic aqueous solution 14 infeeds the solution channel between roller 12 and main pole 13a, the 13b radially by narrow slit 16 from solution supply port 15.

Then, the aluminium sheet of handling well in main electrolytic cell 21 11 carries out electrolytic treatments in impressed current anode groove 22.In this impressed current anode groove 22, impressed current anode 18 is oppositely arranged with aluminium sheet 11, and acidic aqueous solution 14 flows between impressed current anode 18 and aluminium sheet 11.And the electric current that flows in the auxiliary electrode is by thyratron transistor 19a and 19b control.

Main pole 13a and 13b can select with the electrode etc. from graphite, platinum, titanium, niobium, zirconium, stainless steel, fuel battery negative pole, and still, graphite is good especially.As graphite, the impermeability blacklead that the chemical devices that can adopt the open market to sell is used, the blacklead that contains resin pickup etc.

Impressed current anode 18 can from ferrite, yttrium oxide, platinum or with platinum in the valve-use metal top covering of titanium, niobium, zirconium etc. or plating and the known electrode that is used for producing oxygen that constitutes select.

Main electrolytic cell 21 can be parallel with the direct of travel of aluminium sheet 11 with the direction of the supply of the impressed current anode groove 22 interior acidic aqueous solutions that feed, also can be vertical with it.Acidic aqueous solution is preferably in 10～1000cm/sec with respect to the relative velocity of aluminium sheet.

Can connect more than one AC power in the electrolysis unit.Also can use the electrolysis unit more than 2, the electrolytic condition in each device can be identical, also can be different.

After electrolytic treatments finishes, owing in ensuing operation, do not take out treatment fluid, therefore preferably by the nip rolls water squeezing or use nozzle rinse.

Use in the process of above-mentioned electrolysis unit, aluminium sheet in the electrolysis unit is proportional with the energising amount of the acidic aqueous solution that produces anode reaction, for example, based on according to the conductance of (i) acidic aqueous solution and (ii) hyperacoustic transmission speed and (iii) nitric acid and the aluminum ions concentration obtained of temperature, add while the addition of regulating nitric acid and water, owing to from electrolysis unit, overflow gradually, discharge with the acidic aqueous solution of the interpolation volume same amount of nitric acid and water, so preferably keep the concentration stabilize of above-mentioned acidic aqueous solution.

Handle by this electrochemical surface coarsening, can form average diameter on 30～100% area occupation ratio of surface of aluminum plate is 0.5～20 μ m crateriform or cellular pit.The pit that forms makes the non-image part of galley be difficult to produce spot, and has improved anti-India.Electrochemical surface coarsening is handled in order to form high-quality pit on the surface, must note electric weight, and promptly the product of electric current and conduction time is most important condition.Consider that from energy-conservation angle hope can form high-quality pit with electric weight still less.Surface roughness after electrochemical surface coarsening is handled is cut into 0.8mm according to the standard of JISB0601-1994, test and appraisal length 3.0mm, and the arithmetic average roughness of mensuration (Ra) is preferably 0.2～0.7 μ m.

Illustrate in order that below carrying out chemical attack in acidic aqueous solution or alkaline aqueous solution handles, goes surface treatments such as spot processing.Above-mentioned surface treatment respectively before above-mentioned electrochemical surface coarsening is handled or above-mentioned electrochemical surface coarsening handle after, carry out before the anodized described later.But each following surface-treated explanation is just given an example, and the present invention is not limited to each following surface treatment.But, can at random carry out following various processing based on above-mentioned surface treatment.

＜alkaline corrosion is handled 〉

It is in alkaline aqueous solution that alkaline corrosion is handled, and surface of aluminum plate is carried out the processing of chemical attack.Be preferably in above-mentioned electrochemical surface coarsening handle before and carry out respectively afterwards.When the surface coarsening that carried out machinery before electrochemical surface coarsening processing was handled, the surface coarsening processing that is preferably in machinery was carried out afterwards.Can destroy minute structure at short notice because alkaline corrosion is handled, therefore handle more favourable than sour corrosion described later.

Handling the alkaline aqueous solution that adopts as alkaline corrosion can be the aqueous solution more than a kind or 2 kinds that contains in caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, the lithium hydroxide etc.Particularly best based on the aqueous solution of NaOH (caustic soda).Preferably contain the alloying component 0.5～10wt% that contains in aluminium and the aluminium sheet in the alkaline aqueous solution.

The concentration of alkaline aqueous solution is preferably 1～50wt%, is preferably 1～30wt%.

The temperature of the alkaline aqueous solution that alkaline corrosion is handled is preferably 40～80 ℃ at 20～100 ℃, carries out 1～120 second processing, and preferably the processing time is 2～60 seconds.When carrying out after the surface coarsening of machinery is handled, the meltage of aluminium is preferably 5～20g/m ²If, after handling, electrochemical surface coarsening carries out, be preferably 0.01～20g/m ²The corrosive liquid of chemistry is when mixing in the initial alkaline aqueous solution, the most handy liquid sodium hydroxide (caustic soda) and sodium aluminate (sodium aluminate) modulation treatment liquid.

And after the alkaline corrosion processing finishes, owing to do not discharge in the treatment fluid operation below, therefore the most handy nip rolls water squeezing and use nozzle rinse.

When after electrochemical surface coarsening is handled, carrying out the alkaline corrosion processing, can remove the spot that in electrochemical surface coarsening is handled, produces.Such alkaline corrosion is handled and for example can be adopted, and the spy opens the alkaline corrosion method of putting down in writing in sulfuric acid that put down in writing and 15～65wt% 50～90 ℃ contacts in the clear 53-12739 communique method and the public clear 48-28123 communique of spy.

＜sour corrosion is handled 〉

It is in acidic aqueous solution that sour corrosion is handled, and aluminium sheet is carried out the processing of chemical attack, is preferably in above-mentioned electrochemical surface coarsening and carries out after handling.When before above-mentioned electrochemical surface coarsening is handled and/or carry out above-mentioned alkaline corrosion afterwards when handling, also can after handling, alkaline corrosion carry out the sour corrosion processing.

On aluminium sheet, carry out carrying out above-mentioned sour corrosion and handling the intermetallic compound or the monomer Si that can remove the silica that contains surface of aluminum plate after the above-mentioned alkaline corrosion processing, can eliminate the defective that in anodized after this, generates anodic oxidation coating.Its result is called as the fault of adhering to printing ink of the point-like in the non-image part of surface flash shape spot in the time of can preventing to print.

The acidic aqueous solution that the sour corrosion processing is adopted can adopt and contain phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid or their the mixing aqueous acid more than 2 kinds or 2 kinds.Wherein aqueous sulfuric acid is best.The concentration of acidic aqueous solution is preferably 50～500g/L, is preferably 100～500g/L.Also can contain the alloying component that contains in aluminium and the aluminium sheet in the acidic aqueous solution.

The fluid temperature that sour corrosion is handled is 30～90 ℃, is preferably 60～90 ℃, is preferably 70～80 ℃, and the processing time is preferably 1～10 second.This moment, the meltage of aluminium sheet was preferably 0.001～0.2g/m ²And the concentration of acid for example, and sulfuric acid concentration and aluminum ions concentration are preferably selected in the non crystallized scope under the normal temperature.Aluminum ions preferably concentration is 0.1～50g/L, is more preferably 0.1～15g/L, preferably 5～15g/L.

After the sour corrosion processing finishes, owing to do not discharge treatment fluid in the operation below, therefore the most handy nip rolls water squeezing and use nozzle rinse.

＜go spot to handle 〉

When before above-mentioned electrochemical surface coarsening is handled and/or carry out above-mentioned alkaline corrosion afterwards when handling, because handling generally, alkaline corrosion can form spot in surface of aluminum plate, therefore be preferably in alkaline corrosion and fluoridize the above-mentioned spot of acid leach solution of hydracid or their mixed acid more than 2 kinds or 2 kinds with containing phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, hydrofluoric acid, boron after handling, carry out the so-called spot that goes and handle.In addition, after alkaline corrosion was handled, sour corrosion was handled and is gone spot to carry out that any one is just enough among handling.

The concentration of acid solution is preferably 1～500g/L, is preferably 1～300g/L.Also can be dissolved with the alloying component that contains in aluminium and the aluminium sheet totally 0.001～50g/L in the acid solution, be preferably 0.001～15g/L.

The temperature of acid solution is preferably 20 ℃～95 ℃, is preferably 30～70 ℃.Processing time is preferably 1～120 second, is preferably 2～60 seconds.

Remove spot treatment fluid (acid solution) owing to can adopt the waste liquid of the acidic aqueous solution of using in the above-mentioned electrochemical surface coarsening processing, therefore can reduce waste liquid amount.

Go after the spot processing finishes, owing to do not discharge in the treatment fluid operation below, therefore the most handy nip rolls water squeezing and use nozzle rinse.

As these surface-treated combinations, the preferred scheme of expression below.

At first, carry out the surface coarsening of machinery and handle and/or the alkaline corrosion processing, after this go spot to handle.Then, use the electrochemical surface roughening treatment of electrolyte, after this 1. alkaline corrosion handle and continuous with it go spot handle, 2. with the electrochemical surface roughening treatment of electrolysis of hydrochloric acid liquid and continuous with it alkaline corrosion processing, go spot to handle this 1., 2. to carry out any one or two among both and all carry out.

＜anodized 〉

The aluminium sheet that has carried out various processing is as mentioned above as required carried out anodized.

Anodized can adopt method existing in this field.Specifically, in the aqueous solution or non-aqueous solution that form more than 2 kinds or 2 kinds alone or in combination of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid etc., in aluminium sheet, feed direct current or alternating current, can form anodic oxidation coating in surface of aluminum plate.

The condition of anodized has various variations according to the electrolyte that uses, and therefore can not determine, but the concentration of general electrolyte is 1～80wt% that fluid temperature is 5～70 ℃, is preferably 25～55 ℃ without exception, and current density is 0.5～70A/dm ², be preferably 15～60A/dm ², voltage is 1～200V, electrolysis time is 1～1000 second, is preferably 5～60 seconds.

In these anodized, put down in writing in the specification that No. the 1412768th, UK Patent Application in sulfuric acid electrolyte with high current density carry out putting down in writing in the method for anodized and No. 3511661 specification of United States Patent (USP) to make the anode oxidative treatment method of electrobath with phosphoric acid better.Also can carry out in sulfuric acid, carrying out in phosphoric acid, carrying out again after the anodized multistage anodized of anodized etc.

Among the present invention, anodic oxidation coating is preferably 1.0g/m because it is difficult to damage and anti-seal ²More than, quite a lot of again is 1.5g/m ²More than, 2.0g/m more preferably ²More than, 3.0g/m preferably ²More than, and, need consider great energy, 100g/m in order to form thick tunicle ²Below proper, be preferably 40g/m ²Below, quite a lot of again is 20g/m ²Below, be more preferably 15g/m ²Below, 10g/m preferably ²Below.

Be formed with the trickle pit of what is called " micropore " on the surface of anodic oxidation coating.The density of the micropore on the anodic oxidation coating can be adjusted according to the treatment conditions of suitable selection.

Among the present invention, the porosity of anodic oxidation coating is preferably 20～70%, and more preferably 30～60%, be preferably 40～50%.The porosity of anodic oxidation coating obtains speed effect preferably in the thermal diffusion that can fully suppress more than 20% to aluminium support body.The porosity of anodic oxidation coating is in the dirty problem that rises that can more be difficult to cause non-image part below 70%.

The porosity of anodic oxidation coating can be obtained by following formula.

Porosity (%)=[1-(oxide film thereon density/3.98)] * 100

Herein, the density (g/cm of oxide film thereon ³) be to obtain by [thickness of the weight/oxide film thereon of the oxide film thereon in the per unit area].And 3.98 are density (g/cm of aluminium oxide in the chemical handbook ³).

Surface apertures is preferably 0～15nm, and more preferably 0～12nm is preferably 0～10nm.

For anodic oxidation coating, if necessary,, the porosity of anodic oxidation coating and surface apertures are fallen in the above-mentioned scope by carrying out following reaming processing, sealing of hole processing etc.

＜reaming is handled 〉

Among the present invention, in order reaching the porosity of anodic oxidation coating to be adjusted in the suitable scope, to be reduced the purpose of pyroconductivity, after anodized, the reaming that preferably enlarges the aperture of micropore is handled.This reaming is handled by the aluminium base that anodic oxidation coating is formed and is immersed in acidic aqueous solution or the alkaline aqueous solution, dissolves anodic oxidation coating, thereby enlarges the aperture of micropore.The meltage of anodic oxidation coating 0.01～20g/m more fortunately during reaming is handled ²Scope in carry out, better be 0.1～5g/m ², be preferably 0.2～4g/m ²

When using acidic aqueous solution during reaming is handled, preferably adopt the inorganic acid of sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid etc. or the aqueous solution of their mixture.The concentration of acidic aqueous solution is preferably 10～1000g/L, and quite a lot of again is 10～500g/L, and more preferably 20～500g/L is preferably 20～100g/L.The temperature of acidic aqueous solution is preferably 10～90 ℃, more preferably 30～70 ℃, is preferably 40～70 ℃.The time of soaking in acidic aqueous solution is preferably 1～300 second, more preferably 2～100 seconds, is preferably 10～60 seconds.

On the other hand, when adopting alkaline aqueous solution during reaming is handled, preferably from the group that NaOH, potassium hydroxide and lithium hydroxide constitute, select at least one alkaline aqueous solution to use.The pH value of alkaline aqueous solution is preferably 10～13, and better is 11～13, and more preferably 11.5～13.0, be preferably 11.5～12.5.The temperature of alkaline aqueous solution is preferably 10～90 ℃, is preferably 30～50 ℃.The time of soaking in alkaline aqueous solution is preferably 1～500 second, is preferably 2～100 seconds.

＜sealing of hole is handled 〉

Among the present invention, preferably the aluminium support body that obtains as mentioned above anodic oxidation coating being set carries out the sealing of hole processing.

Sealing of hole handle tunicle with for example, carrying out the electro-deposition sealing of hole when handling, form from the bottom of micropore, and carrying out the steam sealing of hole when handling, form from the top of micropore, the mode of handling according to sealing of hole forms the method difference that sealing of hole is handled tunicle.

Be applicable to that sealing of hole of the present invention handles the hole of not sealing anodic oxidation coating inside, and the top of closed porosity only.

The sealing of hole that the present invention adopts is handled and can be adopted the spy to open flat 4-176690 communique and the special sealing of hole processing of being willing to the anodic oxidation coating of carrying out with pressure (hydraulic) water steam and hot water of record in flat 10-106819 number the specification (spy opens flat 11-301135 communique).In addition, also can adopt the known methods such as phosphatic hot water treatment that silicate processing, the processing of the bichromate aqueous solution, nitrite treatments, acetic acid ammonium salt are handled, the electro-deposition sealing of hole is handled, triethanolamine is handled, denier is handled and contained to the carbonic acid barium salt.

Specifiable is that the method for inorganic thin film for example is set by sputter, CVD method etc.Can be used as the compound that inorganic thin film uses, specifiable is for example oxide, nitride, silicide, carbide.In addition, not limiting only a kind ofly, also can be mixture.

Concrete specifiablely be, for example aluminium oxide, silica, titanium oxide, zirconia, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, chromium oxide; Aluminium nitride, silicon nitride, titanium nitride, zirconium nitride, hafnium nitride, vanadium nitride, niobium nitride, tantalum nitride, molybdenum nitride, tungsten nitride, chromium nitride, silicon nitride, boron nitride; Titanium silicide, zirconium silicide, hafnium suicide, vanadium silicide, niobium silicide, tantalum silicide, molybdenum silicide, tungsten silicide, chromium silicide; Titanium boride, zirconium boride, hafnium boride, vanadium boride, niobium (Nb) boride, tantalum boride, molybdenum boride, tungsten boride, chromium boride; Aluminium carbide, carborundum, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, ramet, molybdenum carbide, tungsten carbide, chromium carbide.

Wherein being fit to sealing of hole processing of the present invention is that the atomic sealing of hole of putting down in writing in the special 2001-9871 of the hope specification that passes through is handled.

Handle by atomic sealing of hole and can be provided with by average grain diameter 8～800nm, preferred average grain diameter 10～500nm, the more preferably particle layer formed of the particle of average grain diameter 10～150nm.If the average grain diameter of particle is more than 8nm, it is less that particle enters the inner possibility of the micropore that exists in the anodic oxidation film, can fully obtain high-sensitive effect.If the average grain diameter of particle is abundant with the adaptation of heat sensing layer below 800nm, anti-seal is good.The thickness of particle layer is preferably 8～800nm, more preferably 10～500nm.

Can be used for the particle among the present invention, pyroconductivity is preferably below the 60W/ (mK), more preferably below the 40W/ (mK), is preferably especially below 0.3～10W/ (mK).If pyroconductivity below 60W/ (mK), can fully suppress the thermal diffusion to aluminium support body, fully obtain high-sensitive effect.

The method that particle layer is set limits especially, and preferred specifiable is for example to use the method that contains electrolyte, use direct current or alternating current electrolysis processing aluminium support body that average grain diameter is the hydrophilic particles of 8～800nm.As the waveform that can be used for the alternating current in the above-mentioned electrolytic treatments, specifiable is sine wave, square wave, triangular wave, trapezoidal wave etc.In addition, the frequency of alternating current is considered from the cost aspect that makes supply unit, is preferably 30～200Hz, more preferably 40～120Hz.When the trapezoidal wave that uses as AC current waveform, electric current is respectively 0.1～2msec preferably from the 0 time tp that reaches peak value, is more preferably 0.3～1.5msec.If above-mentioned tp is not enough 0.1msec, the situation that supply voltage that must be bigger when having impedance influence power circuit, current waveform rising, the equipment cost of power supply uprise.

As hydrophilic particles, preferably with Al ₂O ₃, TiO ₂, SiO ₂And ZrO ₂Use more than 2 kinds alone or in combination.Electrolyte is above-mentioned hydrophilic particles to be suspended in water etc. make content obtain for 0.01 whole～20wt%.In order to make negative or positive electrode have electric charge, electrolyte also can be adjusted pH by for example adding sulfuric acid etc.Electrolytic treatments is for example being used direct current, is being used as negative electrode under the voltage of above-mentioned electrolyte at 10～200V with aluminium support body and carry out under 1～600 second condition.

According to this method,, can stop up its outlet simultaneously in the inner residual porosity of micropore that is present on the anodic oxidation film.

In addition, as the method that particle layer is set, preferred especially specifiable be make above-mentioned aluminium support body be immersed in to contain in the solution that average grain diameter is 8～800nm hydrophilic particles method and on above-mentioned aluminium support body coating contain the method that average grain diameter is the solution of 8～800nm hydrophilic particles.According to these methods,, can stop up its outlet simultaneously in the inner residual porosity of micropore that is present on the anodic oxidation film.

In addition, according to these methods, compare with the method for using electrolytic treatments, the spot-resistant of the lithographic plate that obtains is good.Can determine that also the particle layer that obtains by electrolytic treatments is inhomogeneous slightly, not stop up fully at a part of micropore middle outlet that is present on the anodic oxidation film.In contrast, extremely even by the particle layer that dipping or coating obtain, stopped up equably in the outlet that is present in the micropore on the anodic oxidation film.Therefore, as the method that particle layer is set, use the situation of above-mentioned dipping or coating can obtain the better lithographic plate of spot-resistant than the situation of using electrolytic treatments.

As hydrophilic particles, preferably with colloidal silicon dioxide, alumina sol, Al ₂O ₃, TiO ₂, SiO ₂And ZrO ₂Use more than 2 kinds alone or in combination.In the solution that uses in impregnation process and the coating content of above-mentioned hydrophilic particles be preferably whole 0.01wt% above, more preferably more than the 0.05wt%, and preferred 10wt% is following, more preferably below the 5wt%.

The fluid temperature of the solution that uses in the impregnation process is preferably more than 10 ℃, more preferably more than 30 ℃, and preferred below 100 ℃, more preferably below 80 ℃.In addition, the processing time of impregnation process is preferably more than 1 second, more preferably more than 2 seconds, and preferred below 120 seconds, more preferably below 30 seconds.

As the method for coating, specifiablely be that for example rod is coated with, spin coating, spraying, the coating of curtain membrane type, dip-coating, air-blade type coating, blade type coating, roller coating.Wherein preferred spin coating, rod are coated with.

Method for sealing, except above-mentioned, specifiable is inject process, vapor deposition treatment, sputter, ion plating, spraying plating, gold-plated etc., but limits especially.

As concrete processing method, specifiable be for example by coating be provided with the spy open put down in writing in the clear 60-149491 communique by contain at least one amino and be selected from that the compound of at least one group in the group of the group of carboxyl and salt thereof and sulfo group and salt thereof forms layer, the spy open that the compound by being selected from the compound that contains at least one amino and at least one hydroxyl and salt thereof put down in writing in the clear 60-232998 communique forms layer, the spy opens the phosphatic layer of putting down in writing in the clear 62-19494 communique that contains, the spy open put down in writing in the clear 59-101651 communique by the method that contains layer that at least a kind of monomeric unit that contains sulfo group forms as the macromolecular compound of repetitive etc. in the molecule.

In addition, also specifiable is the method that the layer that is selected from following compound is set: carboxymethyl cellulose; Dextrin; Arabic gum; 2-ciliatine etc. contains amino phosphonic acid based; Can contain organic phospho acids such as substituent phenyl-phosphonic acid, naphthalene phosphonic acids, alkyl phosphonic acid, glycerine phosphonic acids, methylenediphosphonate, ethylidene diphosphonic acid; Can contain organophosphorus esters such as substituent phenyl phosphate, Naphthyl phosphate, alkylphosphonate, phosphoglyceride; Can contain organic hypophosphorous acid such as substituent benzene hypophosphorous acid, naphthalene hypophosphorous acid, alkyl hypophosphorous acid, glycerine hypophosphorous acid; Amino acids such as glycine, Beta-alanine; The hydrochloride of triethanolamine etc. contains the hydrochloride etc. of the amine of hydroxyl.

In sealing of hole is handled, also can apply and handle the silane coupling agent that contains unsaturated group.As silane coupling agent, specifiable is N-3-(propenyloxy group-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene for example, (3-propenyloxy group propyl group) dimethyl methyl TMOS, (3-propenyloxy group propyl group) methyl dimethoxysilane, (3-propenyloxy group propyl group) trimethoxy silane, 3-(N-allyl amino) propyl trimethoxy silicane, the allyl dimethyl TMOS, allyltriethoxysilane, allyltrimethoxysilanis, 3-cyclobutenyl triethoxysilane, 2-(chloromethyl) allyltrimethoxysilanis, the methacrylamido propyl-triethoxysilicane, N-(3-metacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene, (metacryloxy methyl) dimethylethoxysilane, the metacryloxy MTES, the metacryloxy MTMS, metacryloxy propyl-dimethyl Ethoxysilane, metacryloxy propyl-dimethyl methoxy silane, metacryloxy propyl group methyldiethoxysilane, metacryloxy propyl group methyl dimethoxysilane, metacryloxy propyl group MTES, metacryloxy propyl group MTMS, metacryloxy propyl group three (methoxy ethoxy) silane, methoxyl group dimethyl vinyl silanes, 1-methoxyl group-3-(trimethylsiloxy) butadiene, the styryl ethyl trimethoxy silane, 3-(N-styryl methyl-2-aminoethyl amino)-propyl trimethoxy silicane hydrochloride, vinyl-dimethyl base oxethyl silane, vinyl diphenyl Ethoxysilane, the vinyl methyldiethoxysilane, the vinyl methyl dimethoxysilane, O-(ethyleneoxy ethyl)-N-(triethoxysilylpropyltetrasulfide) urethanes, VTES, vinyltrimethoxy silane, vinyl three tert-butoxy silane, vinyl silane triisopropoxide, vinyl triple phenoxyl silane, vinyl three (2-methoxy ethoxy) silane, diallyl aminopropyl methoxy silane.Wherein preferably contain the reactive fast methacryl of unsaturated group, the silane coupling agent of acryloyl group.

In addition, the specifiable spy of being opens the collosol and gel coating of putting down in writing in the flat 5-50779 communique and handles, the coating of the phosphonic acid based of putting down in writing in the Te Kaiping 5-246171 communique is handled, Te Kaiping 6-234284 communique, the raw-material method that anti-coating is used is handled in the coating of putting down in writing in the flat 6-230563 communique of Te Kaiping 6-191173 communique and Te Kai of passing through, the processing of the phosphonic acid based of putting down in writing in the Te Kaiping 6-262872 communique, the coating of putting down in writing in the Te Kaiping 6-297875 communique is handled, the anode oxidative treatment method of putting down in writing in the Te Kaiping 10-109480 communique, special impregnation process methods of being willing to record in flat 10-252078 specification (spy opens the 2000-81704 communique) and the special flat 10-253411 specification of hope (spy opens the 2000-89466 communique) etc. can be used any method.

＜usefulness contains the processing of the aqueous solution of inorganic fluorine compounds and silicate compound 〉

In the present invention, handle, can handle with the aqueous solution that contains inorganic fluorine compounds and silicate compound as preferred sealing of hole.Thus, when making lithographic plate, can obtain the supporter of the good lithographic printing plate-use of spot-resistant.

As spendable inorganic fluorine compounds among the present invention, what be fit to enumerate is metal fluoride.

Concrete specifiablely be, for example sodium fluoride, potassium fluoride, calcirm-fluoride, magnesium fluoride, hexafluoro zirconium sodium, hexafluoro zirconium potassium, hexafluoro sodium titanate, hexafluoro potassium titanate, hexafluoro hydracid zirconium, hexafluoro hydracid titanium, hexafluoro zirconium ammonium, ammonium hexa-fluorotitanate, hexafluorosilicic acid, nickel fluoride, ferric flouride, fluorinated phosphate, fluorinated phosphate ammonium.

In addition, as spendable silicate compound among the present invention, specifiable is silicic acid, silicate, and what wherein be fit to enumerate is alkali silicate.

Concrete specifiablely be, for example sodium metasilicate, potassium silicate, lithium metasilicate.Wherein preferred sodium metasilicate, potassium silicate.

Sodium metasilicate is specifiable to be, for example No. 3 sodium metasilicate, No. 2 sodium metasilicate, No. 1 sodium metasilicate, sodium orthosilicate, sodium sesquisilicate, sodium metasilicate.Potassium silicate is specifiable to be, for example No. 1 potassium silicate.In addition, can also use the aluminium that contains aluminium for silicate, contain the borosilicate of boric acid.

Silicic acid is specifiable to be, orthosilicic acid, metasilicic acid, inclined to one side two silicic acid, inclined to one side three silicic acid, inclined to one side tetrasilicic acid.

Each compound concentrations in the aqueous solution, for inorganic fluorine compounds, consider to be preferably more than the 0.01wt% from the sealing of hole aspect of anodic oxidation film, more preferably more than the 0.05wt%, more than the preferred especially 0.1wt%, consider to be preferably below the 10wt% from the spot-resistant aspect in addition, more preferably below the 1wt%, below the preferred especially 0.5wt%.

In addition, for silicate compound, consider from the spot-resistant aspect, be preferably 0.01wt% above, more preferably more than above, the preferred especially 1wt% of 0.1wt%, consider to be preferably below the 10wt% from anti-seal aspect in addition, more preferably below the 7wt%, below the preferred especially 5wt%.

The ratio of each compound limits especially in the aqueous solution, and the weight ratio of inorganic fluorine compounds and silicate compound is preferably 5: 95～and 95: 5, more preferably 20: 80～80: 20.

In addition, contain the aqueous solution of inorganic fluorine compounds and silicate compound,, also can contain the hydroxide such as NaOH, potassium hydroxide, lithium hydroxide of appropriate amount in order to improve pH.Wherein preferred NaOH, potassium hydroxide.

In addition, contain the aqueous solution of inorganic fluorine compounds and silicate compound, also can contain alkali earth metal salt or 4 families (IVA family) slaine.As alkali earth metal salt, specifiable is nitrate such as calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate for example; Sulfate; Hydrochloride; Phosphate; Acetate; Bromate; Water soluble salts such as borate.As 4 families (IVA family) slaine, but for example can enumerate titanium tetrachloride, titanium trichloride, titanium potassium fluoride, bromic acid titanium potassium, titanium sulfate, titanium tetra iodide,, chloride oxidation zirconium, zirconium dioxide, zirconyl hydroxychloride, zirconium chloride.These alkali earth metal salts and 4 families (IVA family) slaine can use more than 2 kinds alone or in combination.

In addition, the temperature of the aqueous solution is preferably more than 10 ℃, more preferably more than 20 ℃, and preferred below 100 ℃, more preferably below 80 ℃.

In addition, the aqueous solution be preferably pH8 above, more preferably more than the pH10, and preferred pH13 is following, more preferably below the pH12.

Method with the aqueous solution that contains inorganic fluorine compounds and silicate compound is handled limits especially, and specifiable is for example infusion process, gunite.These methods both can be independent 1 time or repeatedly use, and also can make up more than 2 kinds and use.

Wherein, preferred infusion process.When using infusion process to handle, the processing time is preferably more than 1 second, more preferably more than 3 seconds, and preferred below 600 seconds, more preferably below 120 seconds.

＜hydrophilic surface is handled 〉

In the present invention, also can carry out hydrophilic surface and handle by aluminium support body being immersed in the aqueous solution that contains hydrophilic compounds more than a kind again.As hydrophilic compounds, be fit to enumerate be for example polyvinyl phosphoric acid, potassium zirconium fluoride, phosphate/inorganic fluorine compounds, contain sulfonic compound, saccharide compound, silicate compound.What wherein be fit to is polyvinyl phosphoric acid, silicate compound.It is the most suitable that what enumerate is silicate compound.

Contain can contain in the sulfonic compound aromatic sulphonic acid, its formaldehyde condensation products, its derivative, with and salt.

As aromatic sulphonic acid; specifiable is for example phenolsulfonic acid, catechol sulfonic acid, resorcinol sulfonic acid, benzene sulfonic acid, toluenesulfonic acid, lignosulfonic acid, naphthalene sulfonic acids, acenaphthene-5-sulfonic acid, phenanthrene-2-sulfonic acid, benzaldehyde-2 (or 3)-sulfonic acid, benzaldehyde-2; 4 (or 3,5)-disulfonic acid, acrinyl sulfonic acid class, sulfo group benzoic acid, sulfanilic acid, naphthonic acid, taurine.Wherein preferred benzene sulfonic acid, naphthalene sulfonic acids, lignosulfonic acid.The formaldehyde condensation products of also preferred in addition benzene sulfonic acid, naphthalene sulfonic acids, lignosulfonic acid.

In addition, these also can be used as the sulfonate use.Specifiable for example is, sodium salt, sylvite, lithium salts, calcium salt, magnesium salts.Wherein particular certain cancers, sylvite.

The pH that contains the aqueous solution with sulfonic group compound is preferably 4～6.5, can use sulfuric acid, NaOH, ammonia etc. to be adjusted to above-mentioned pH scope.

Can contain monosaccharide and sugar alcohol, oligosaccharides, polysaccharide and glucosides in the saccharide compound.

As monosaccharide and sugar alcohol thereof, specifiable is triose class and glycitols thereof such as glycerine for example; Tetrose such as threose, erythrite and glycitols thereof; Pentose such as arabinose, arabitol and glycitols thereof; Hexose such as glucose, D-sorbite and glycitols thereof; D-glycerine-D-galactoheptose, D-glycerine-D-galactoheptose alcohol heptose and glycitols thereof such as (ガ ラ Network ト ヘ プ チ ト-Le); D-is red-octose and glycitols thereof such as D-gala octose alcohol; D-is red-L-Network Le コ-ノ ヌ ロ-ス nonoses and glycitols thereof such as (glyco-nonurose).

As oligosaccharides, specifiable is disaccharides such as sucrose, trehalose, lactose for example; Three carbohydrates such as melitriose.

As polysaccharide, specifiable is for example amylose, ア ラ PVC Na Application (arabinan), cyclodextrin, alginic acid fibre element.

In the present invention, so-called " glucosides " is meant sugar moieties and the aglucone branch compound by combinations such as ester bonds.

Glucosides can be according to the aglucone classification.Specifiable is for example APG, phenol glucosides, coumarin glycoside, Hydroxycoumarin glucosides, flavonoids glucosides, anthraquinone glucosides, triterpene glucosides, steroid glucosides, mustard oil glycoside.

As sugar moieties, specifiable is above-mentioned monosaccharide and sugar alcohol thereof; Oligosaccharides; Polysaccharide.Wherein preferred monosaccharide, oligosaccharides, more preferably monosaccharide, disaccharides.

As the example of preferred glucosides, specifiable is the compound of following formula (I) expression.

Change 1

In the above-mentioned formula (I), R represents that carbon number is 1～20 straight chain or alkyl, the alkenyl or alkynyl that contains side chain.

It as carbon number 1～20 alkyl, specifiable is for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, these both can be straight chains, also can contain side chain, also can be cyclic alkyl in addition.

As carbon number is 1～20 thiazolinyl, and specifiable is pi-allyl, 2-cyclobutenyl, and these both can be straight chains, also can contain side chain, also can be the ring-type thiazolinyl in addition.

As carbon number is 1～20 alkynyl, and specifiable is 1-pentynyl for example, and these both can be straight chains, also can contain side chain, also can be the ring-type alkynyl in addition.

As the particular compound of above-mentioned formula (I) expression, specifiable is for example methyl glucosamine, ethyl cyclophosphadenosine glycoside, propyl group glucoside, isopropyl glucoside, butyl glucoside, isobutyl group glucoside, n-hexyl glucoside, octyl glucoside, octyl glucoside, Plantacare 818,2-ethylhexyl glucoside, 2-amyl group nonyl glucoside, 2-hexyl Plantacare 818, lauryl glucoside, myristyl glucoside, stearyl glucoside, cyclohexyl glucoside, 2-butynyl glucoside.These compounds can be a kind of glucosides of glucosides, also can be the hemiacetal hydroxyl of glucose and the material that other compounds are combined into the ether shape, for example can make glucose and alcohols reaction obtain by known method.The part of these alkyl glucosides is to be sold as trade name グ Le コ Port Application (GLUCOPON) by Henkel society of Germany's (De イ Star), can use them among the present invention.

Other examples as preferred glucosides, specifiable is for example saponarin, rutin sophorin trihydrate, aurantiamarin methyl chalcone, aurantiamarin, Na リ ジ Application (narijin) hydrate, phenol-β-D-glucopyranoside, salicin, 3 ', 5,7-methoxyl group-7-rutinoside.

The pH that contains the aqueous solution of saccharide compound is preferably 8～11, can use potassium hydroxide, sulfuric acid, carbonic acid, sodium carbonate, phosphoric acid, sodium phosphate etc. to be adjusted to above-mentioned pH scope.

The concentration of the aqueous solution of polyvinyl phosphonic acids is preferably 0.01～10wt%, more preferably is 0.1～5wt%, 0.2～2.5wt% more preferably.The temperature of dipping is preferably 10～70 ℃, more preferably 30～60 ℃.Dip time is preferably 0.5 second～and 10 minutes, more preferably be 1～30 second, more preferably 1～20 second.

In addition, the concentration that contains the aqueous solution of sulfonic group compound is preferably 0.02～0.2wt%.Dipping temperature is preferably 60～100 ℃.Dip time is preferably 1～300 second, more preferably 10～100 seconds.

In addition, the concentration that contains the aqueous solution of saccharide compound is preferably 0.5～10wt%.Dipping temperature is preferably 40～70 ℃.Dip time is preferably 2～300 seconds, more preferably 5～30 seconds.

As the hydrophilicity-imparting treatment among the present invention, except above-mentioned, can also adopt known method and condition.As known method and condition, specifiable method, the spy who is the use potassium zirconium fluoride put down in writing in the method handled of the use alkali silicate (alkali silicate) for example put down in writing in No. 2714066 specification of United States Patent (USP) and No. 3181461 specification, the special public clear 36-22063 communique is handled opens method, spy that the aqueous solution that the use of putting down in writing in the flat 9-244227 communique contains phosphate and inorganic fluorine compounds handles and opens the 2000-81704 communique and specially open the method that the aqueous solution that the use of putting down in writing in the 2000-89466 communique contains titanium and fluorine is handled.

Alkali metal silicate aqueous solution handle by at preferred concentration be 0.01～30wt%, more preferably be 0.01～10wt%, more preferably 0.1～10wt%, more preferably 0.5～5wt%, 25 ℃ of following pH are preferably in the aqueous solution of 10～13 alkali silicate, preferred 30～100 ℃, more preferably 50～90 ℃ down dipping supporter preferred 0.5～40 second, more preferably carry out for 1～20 second.Treatment conditions such as the concentration of above-mentioned alkali silicate, pH, temperature, processing time can suitably be selected.If the pH of alkali metal silicate aqueous solution is lower than 10, the easy gelation of solution, if pH is higher than 13 in addition, particle layer and anodic oxidation film may dissolve, so this point should be noted that.

The alkali silicate that uses during hydrophilic surface is handled, specifiable is for example as the above-mentioned cited material of alkali silicate that uses in the aqueous solution of inorganic fluorine compounds and silicate compound that contains.

The aqueous solution of alkali silicate in order to improve pH, also can contain the hydroxide such as NaOH, potassium hydroxide, lithium hydroxide of appropriate amount.Wherein preferred NaOH, potassium hydroxide.

In addition, the aqueous solution of alkali silicate also can contain alkali earth metal salt or 4 families (IVA family) slaine.As alkali earth metal salt, specifiable is for example as the above-mentioned cited material of alkali earth metal salt that also can contain in the aqueous solution of inorganic fluorine compounds and silicate compound that contains.Alkali earth metal salt and 4 families (IVA family) slaine can be used singly or two or more kinds in combination.The consumption of these slaines is preferably 0.01～10wt%, 0.05～5.0wt% more preferably.

The potassium zirconium fluoride aqueous solution handle by be 0.1～10wt% at preferred concentration, more preferably in the potassium zirconium fluoride aqueous solution of 0.5～2wt%, preferred 30～80 ℃ down the dipping supporters carry out preferred 60～180 seconds.

In addition, as the inorganic fluorine compounds that uses in the hydrophilic surface processing, what be fit to enumerate is metal fluoride.

Concrete specifiable is for example as the above-mentioned cited material of inorganic fluorine compounds that uses in the aqueous solution of inorganic fluorine compounds and silicate compound that contains.

Supporter is flooding to the aqueous solution that contains these hydrophilic compounds washings such as water, drying.

By above-mentioned hydrophilic surface processing, can solve and the printing pollution problems such as set-off (adhering to printing ink) deterioration that replace generation by the processing speed raising of the reaming after the anodized (raising of anti-seal under the situation of negativity recording layer).Promptly there are the following problems: because the aperture enlarges, when printing, particularly printing machine stop, when beginning to print again after being placed on lithographic plate on the printing machine, be easy to generate the phenomenon (set-off (adhering to printing ink) deterioration) that printing ink is difficult to remove, if handle but implement hydrophilic surface, can alleviate the problems referred to above.

＜priming coat 〉

In the present invention, before by infrared laser exposure the recording layer that can write being set on the aluminium support body that so obtains, inorganic bottom coating and organic priming coat of water-soluble metal salt such as Firebrake ZB for example and so on can be set also as required.

As the organic compound that uses in organic priming coat, specifiable is carboxymethyl cellulose for example; Dextrin; Arabic gum; Contain sulfonic polymer and copolymer on the side chain; Polyacrylic acid; 2-ciliatine etc. contains amino phosphonic acid based; Can contain organic phospho acids such as substituent phenyl-phosphonic acid, naphthalene phosphonic acids, alkyl phosphonic acid, glycerine phosphonic acids, methylenediphosphonate, ethylidene diphosphonic acid; Can contain organic phosphoric acids such as substituent benzenephosphonic acid, naphthalene phosphoric acid, alkyl phosphoric acid, phosphoglycerol; Can contain organic hypophosphorous acid such as substituent benzene hypophosphorous acid, naphthalene hypophosphorous acid, alkyl hypophosphorous acid, glycerine hypophosphorous acid; Amino acids such as glycine, Beta-alanine; The hydrochloride of triethanolamine etc. contains the hydrochloride of the amine of hydroxyl; Weld.These can use separately, also can mix more than 2 kinds and use.

Organic priming coat can use following method setting.Promptly, can be coated on the aluminium support body and the dry method that organic priming coat is set by the solution that above-mentioned organic compound is dissolved in organic solvent such as water or methyl alcohol, ethanol, methyl ethyl ketone or these the mixed solvent, with aluminium support body be immersed in the solution that above-mentioned organic compound is dissolved in organic solvent such as water or methyl alcohol, ethanol, methyl ethyl ketone or these mixed solvent, washing such as water and drying are provided with the method for organic priming coat to the above-mentioned organic compound of absorption then.

In preceding a kind of method, the concentration of having dissolved the solution of above-mentioned organic compound is preferably 0.005～10wt%.The method of coating does not limit especially, can use any methods such as rod is coated with, spin coating, spraying, the coating of curtain membrane type.In addition, in a kind of method in back, the concentration of having dissolved the solution of above-mentioned organic compound is preferably 0.01～20wt%, 0.05～5wt% more preferably, dipping temperature is preferably 20～90 ℃, more preferably 25～50 ℃, and dip time is preferably 0.1 second～and 20 minutes, more preferably 2 seconds～1 minute.The solution that uses in these methods also can pass through alkaline matter and acidic materials adjusting pH such as hydrochloric acid, phosphoric acid such as ammonia, triethylamine, potassium hydroxide, uses in the scope of pH1～12.

The dried overlay capacity of organic priming coat is preferably 2～200mg/m ², 5～100mg/m more preferably ²If in above-mentioned scope, it is better that anti-seal becomes.

In addition, the spy intermediate layer of opening the macromolecular compound of putting down in writing in the flat 11-109637 communique that contains acidic group and Weng Ji also can be used as priming coat and uses.

＜back coating 〉

On according to the above-mentioned supporter that obtains, make in the original edition of lithographic printing plate, even can not damage recording layer for overlapping yet, also can be as required cover layer that reverse side (face of recording layer side is not set) setting is made up of organic high molecular compound (below be also referred to as " back coating ").

As the principal component of back coating, preferred use that to be selected from glass transition temperature be at least a resin in saturated copolymer polyester resin, phenoxy resin, polyvinyl acetal resin and the vinylidene fluoride copolymer resins more than 20 ℃.

Saturated copolymer polyester resin is made of dicarboxylic acid units and diol units.As dicarboxylic acid units, specifiable is aromatic dicarboxylic acids such as phthalic acid, terephthalic acid (TPA), M-phthalic acid, tetrabromo-benzene dioctyl phthalate, tetrachloro-phthalic acid for example; Adipic acid, azelaic acid, butanedioic acid, oxalic acid, suberic acid, decanedioic acid (acid of セ バ チ Application), malonic acid, 1, saturated aliphatic dicarboxylic acids such as 4-cyclohexane diacid.

Back coating can also suitably contain be useful on painted dyestuff and pigment, be used to improve the diazo resin that constitutes with the silane coupling agent of supporter adaptation, by diazol, dimethyl siloxane of organic phospho acid, organic phosphoric acid, cation property copolymer, the silicone compounds that constitutes as the normally used wax of lubricant, higher fatty acids, higher fatty acid amides, by dimethyl siloxane, modification, polyethylene powders etc.

The thickness of back coating even there is not packing paper, only just passable otherwise damage recording layer described below basically, is preferably 0.01～8 μ m.If thickness less than 0.01 μ m is difficult to prevent the scratch of recording layer when aiming at the original edition of lithographic printing plate operation.In addition, if thickness surpasses 8 μ m because in press, the medicine that uses of lithographic plate periphery, the back coating expanded thickness changes sometimes, external pressure changes the printing characteristic variation.

As the method that back coating is set at the supporter reverse side, can use various methods.Specifiable for example is, the above-mentioned back coating of dissolving applies and dry method with composition and with the solution coating or with emulsified dispersed liquid in appropriate solvent; The thing that will be pre-formed the film shape with binding agent and heat is bonded in the method on the supporter; Form fused films, be bonded in the method on the supporter with melt extruding machine.Based on guaranteeing suitable thickness, most preferably in appropriate solvent, dissolve the method for back coating with composition, drying.In the method, can be separately or mix as specially open the organic solvent put down in writing in the clear 62-251739 communique, use as solvent.

In the making of original edition of lithographic printing plate, both can on supporter, at first be provided with reverse side back coating and the surface recording layer in any one, also can be provided with two simultaneously in addition.

＜recording layer 〉

Original edition of lithographic printing plate of the present invention can make by the recording layer that the infrared laser exposure writes by being provided with on the aluminium support body that so obtains.

The heat sensing layer that is used for the present invention is so long as the recording layer that can write by infrared laser exposure limits especially.Specifiable for example is, contain particulate polymer with heat reactivity functional group or comprise the heat sensing layer of microcapsules with heat reactivity functional compounds and contain infrared absorbent and in water insoluble but in alkaline aqueous solution soluble macromolecular compound, the heat sensing layer that can write by infrared laser irradiation.

In original edition of lithographic printing plate of the present invention, recording layer preferably contains:

(a) have the particulate polymer of heat reactivity functional group, or

(b) comprise the heat sensing layer of microcapsules with heat reactivity functional compounds.If use this heat sensing layer, can make developing type original edition of lithographic printing plate on the machine.

Below, for the original edition of lithographic printing plate that obtains by the present invention, exemplify to use and contain particulate polymer or describe the situation that comprises the heat sensing layer of microcapsules with heat reactivity functional compounds with heat reactivity functional group.

Common heat reactivity functional group as above-mentioned (a) and (b); specifiable is the ethene unsaturated group that for example carries out polymerisation (acryloyl group for example; methacryl; vinyl; pi-allyl); carry out NCO or its block body of addition reaction; it is (for example amino that its reaction the other side is promptly contained the functional group of active hydrogen atom; hydroxyl; carboxyl); carry out the epoxy radicals of addition reaction equally; its reaction the other side is promptly amino; carboxyl or hydroxyl; carry out carboxyl and the hydroxyl or the amino of condensation reaction, carry out acid anhydrides and the amino or the hydroxyl of opening.The heat reactivity functional group that is used for the present invention is not limited to these, as long as form chemical bond, also can be the functional group that carries out any reaction.

As heat reactivity functional group suitable in the particulate polymer (a); specifiable for example is, acryloyl group, methacryl, vinyl, pi-allyl, epoxy radicals, amino, hydroxyl, carboxyl, NCO, anhydride group and the group of protecting them.In polymer particle, import heat reactivity functional group, both can carry out in that polymer poly is fashionable, also can after polymerization, utilize high molecular weight reactive to carry out.

Under the situation of the fashionable importing heat reactivity of polymer poly functional group, the preferred monomer that contains heat reactivity functional group that uses carries out emulsion polymerisation or suspension polymerisation.

As the object lesson that contains the heat reactivity monomer, specifiable is allyl methacrylate, allyl acrylate, the metering system vinyl acetate, vinyl acrylate, GMA, glycidyl acrylate, 2-NCO ethyl-methyl acrylate, the blocked isocyanate that forms by its alcohol etc., 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, the 2-hydroxyethylmethacry,ate, acrylic acid, methacrylic acid, maleic anhydride, two functional acrylates, two sense methacrylates.The monomer that contains heat reactivity functional group that is used for the present invention is not limited to these.

As can be with these monomer copolymerizations, do not contain the monomer of heat reactivity functional group, specifiable is for example styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl acetate.The monomer that does not contain heat reactivity functional group that is used for the present invention is not limited to these.

As the high molecular weight reactive that uses under the situation that imports heat reactivity functional group after polymer polymerizing, specifiable is for example international high molecular weight reactive of putting down in writing in No. 96/34316 brochure that discloses.

In the above-mentioned particulate polymer (a), the preferred material that is integrated by heat with the particulate polymer, more preferably its surface is dispersed in material in the water for hydrophily.In addition, the sub-polymer of coated fine particles only, under than the also low temperature of setting temperature the phase corner cut (aerial water droplet) of film during dry the making, the phase corner cut (aerial water droplet) of film is also low during preferably than dry making the under than the also high temperature of setting temperature.

Make the surface of such particulate polymer become hydrophily,, but be not limited to these as long as on the surface of particulate polymer, adsorb hydrophilic polymer or oligomer or hydrophily low molecular compounds such as polyvinyl alcohol, polyethylene glycol.

The setting temperature of particulate polymer (a) is preferably more than 70 ℃, if but consider ageing stability then more preferably more than 100 ℃.

The average grain diameter of particulate polymer (a) is preferably 0.01～20 μ m, 0.05～2.0 μ m more preferably wherein, preferred 0.1～1.0 μ m.In this scope, can obtain good resolution ratio and ageing stability.

The addition of particulate polymer (a) is preferably more than the 50wt% of heat sensing layer solid constituent, more preferably more than the 60wt%.

As heat reactivity functional group suitable in the microcapsules (b), specifiable for example is, polymerism unsaturated group, hydroxyl, carboxyl, carboxylic acid ester groups, anhydride group, amino, epoxy radicals, NCO, isocyanates block body.

As the compound that contains the polymerism unsaturated group, be preferably and contain at least 1, preferred 2 above ethene unsaturated bonds for example acryloyl group, methacryl, vinyl, allylic compound.Such compound group is a well-known compound in this industrial circle, and in the present invention, not being confined to these especially can use.These are that monomer, prepolymer are dimer, trimer and oligomer as chemical form, perhaps their mixture, and their copolymer.

Concrete specifiable for example is, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid), its ester, unsaturated carboxylic acid acid amides.Wherein, be preferably the ester of unsaturated carboxylic acid and aliphatic polyol and the acid amides of unsaturated carboxylic acid and aliphatic polyamine.

In addition, the addition compound product that contains the substituent esters of unsaturated carboxylic acids of nucleophilicity such as hydroxyl, amino, sulfydryl or unsaturated carboxylic acid acid amides and simple function or polyfunctional isocyanate or epoxides, and also be fit to use with the dehydrating condensation product of simple function or polyfunctional carboxylic acids etc.

In addition, contain the addition compound product of the substituent esters of unsaturated carboxylic acids of electrophilicity such as NCO, epoxy radicals or acid amides and simple function or polyfunctional alcohol, amine or mercaptan, and the substitution product that contains the substituent esters of unsaturated carboxylic acids of detachment such as halogen group and tolysulfonyl oxygen base or acid amides and simple function or polyfunctional alcohol, amine or mercaptan is fit to also.

In addition, as other suitable examples, specifiable is the compound that above-mentioned unsaturated carboxylic acid is replaced with unsaturated phosphonic acids or 1-chloro-4-methyl-benzene.

In the polymerizable compound of the ester of unsaturated carboxylic acid and aliphatic polyol, as acrylate, specifiable is ethylene glycol diacrylate for example, the diacrylate triethyleneglycol ester, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, the diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ester, the trimethylolethane trimethacrylate acrylate, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate tetraethylene glycol ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the diacrylate dipentaerythritol ester, five acrylic acid 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 (acryloxy ethyl) chlorinated isocyanurates, the polyester acrylic ester oligomer.

As methacrylate, specifiable is dimethacrylate 1 for example, the 4-butanediol ester, the dimethacrylate triethyleneglycol ester, the dimethacrylate DOPCP, the trimethylolpropane methacrylate, the trimethylolethane methacrylate, GDMA, dimethacrylate 1, the 3-butanediol ester, dimethacrylate hexylene glycol 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, two [p-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two [p-(methacryloxy ethyoxyl) phenyl] dimethylmethane.

As itaconate, specifiable is for example two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acids 1,3-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid tetramethylene glycol esters, two itaconic acid pentaerythritol esters, four itaconic acid sorbitol esters.

As crotonates, specifiable is for example two crotonic acid glycol esters, two crotonic acid tetramethylene glycol esters, two crotonic acid pentaerythritol esters, four crotonic acid sorbitol esters.

As the iso-crotonic acid ester, specifiable is for example two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters, four iso-crotonic acid sorbitol esters.

As maleate, specifiable is for example two maleic acid glycol esters, two maleic acid triethyleneglycol ester, two maleic acid pentaerythritol esters, four maleic acid sorbitol esters.

As other esters, specifiable is that the aliphatic alcohol put down in writing in for example special public clear 46-27926 communique, same 51-47334 communique, the same 57-196231 communique is that ester class and the special clear 59-5240 communique, same 59-5241 communique, spy opened are opened the ester that contains aromatic series pastern bone frame, the spy that put down in writing in the flat 2-226149 communique and opened the amino ester of putting down in writing in the flat 1-165613 communique that contains.

In addition, object lesson as the amide monomer of aliphatic polyamine compound and unsaturated carboxylic acid, specifiable is methylene diacrylamine, methylene DMAA, 1, the own diacrylamine of 6-, 1, the own DMAA of 6-, diethylenetriamines three acrylamides, xyxylene diacrylamine, xyxylene DMAA.

As other preferred acid amides is monomer, and specifiable is for example special monomer of putting down in writing in the clear 54-21726 communique that contains the cyclohexylidene structure of opening.

In addition, the urethanes that uses the addition reaction manufacturing of isocyanates and hydroxyl is that the addition polymerization compound also is fit to, in the polyisocyanate compounds of putting down in writing in the concrete specifiable for example special public clear 48-41708 communique that in 1 molecule, contains 2 above NCOs below the addition unsaturated monomer that contains hydroxyl of formula (II) expression obtain, contain in 1 molecule the urethane compounds of 2 above polymerism unsaturated groups.

CH ₂＝C(R ₁)COOCH ₂CH(R ₂)OH (II)

(wherein, R ₁And R ₂Represent H or CH respectively ₃)

In addition, can be used as also that suitable example enumerates be as the spy open the urethane acrylate put down in writing in clear 51-37193 communique, special fair 2-32293 communique, the same 2-16765 communique and, the urethane compounds of putting down in writing in special public clear 58-49860 communique, same 56-17654 communique, same 62-39417 communique, the same 62-39418 communique that contains oxirane pastern bone frame.

In addition, can also as suitable example enumerate be the spy open clear 63-277653 communique, same 63-260909 communique, spy open put down in writing in the flat 1-105238 communique, molecule contains the polymerizable compound of amino structure and sulfide structure.

As other suitable examples, specifiable is polyfunctional acrylate and the methacrylates such as epoxy acrylate class of opening polyester acrylate class, epoxy resin and the reaction of (methyl) acrylic acid put down in writing in clear 48-64183 communique, special public clear 49-43191 communique, the same 52-30490 communique as the spy.What in addition, can be used as also that suitable example enumerates is the vinyl phosphonate based compound put down in writing in the specific unsaturated compound put down in writing in special public clear 46-43946 communique, special fair 1-40337 communique, the same 1-40336 communique and the flat 2-25493 communique of Te Kai etc.What in addition, also be fit in some cases to enumerate is that the spy opens the compound of putting down in writing in the clear 61-22048 communique that contains perfluoroalkyl.What also be fit in addition exemplify is the material of introducing as light solidity monomer and oligomer in the Japan bonding association will, 20 volumes No. 7 the 300th～308 page (1984).

As suitable epoxide, specifiable for example is, the poly epihydric alcohol base ether of glycerine poly epihydric alcohol base ether, polyethylene glycol diglycidyl ether, polypropylene diglycidyl ether, trimethylolpropane poly epihydric alcohol base ether, sorbierite poly epihydric alcohol base ether, bisphenols or polyatomic phenol or their hydrogenation products.

As suitable isocyanate compound, specifiable is for example toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, polymethylene polyphenyl PIC, xyxylene vulcabond, naphthalene diisocyanate, cyclohexane phenylene vulcabond, IPDI, hexamethylene diisocyanate, cyclohexyl diisocyanate, perhaps uses alcohol or the amine compound with their blocks.

As suitable amines, specifiable is for example ethylenediamine, diethylenetriamines, trien, hexamethylene diamine, propylene diamine, polymine.

As the suitable compound that contains hydroxyl, specifiable is polyalcohol, bis-phenol polyatomic phenols such as for example terminal compound that contains methylol, pentaerythrite.

As the suitable compound that contains carboxyl, specifiable is for example 1,2,4,5-benzenetetracarboxylic acid, 1,2, aliphatic polybasic carboxylic acids such as aromatic series polybasic carboxylic acid, adipic acid such as 4-benzenetricarboxylic acid, phthalic acid.

As suitable acid anhydrides, specifiable is for example 1,2,4,5-pyromellitic anhydride, benzophenone tetracarboxylic anhydride.

As the copolymer of suitable ethene shape unsaturated compound, specifiable is the copolymer of allyl methacrylate for example.Concrete specifiable for example is, allyl methacrylate/methacrylic acid copolymer, allyl methacrylate/ethyl methacrylate copolymers, allyl methacrylate/butyl methacrylate copolymer.

As the method for microencapsulation, known method can be suitable for.For example, specifiable as the manufacture method of microcapsules is No. 2800457 specification of United States Patent (USP), the method of the utilization cohesion of putting down in writing in same No. 2800458 specification, No. 990443 specification of BP, No. 3287154 specification of United States Patent (USP), special public clear 38-19574 communique, same 42-446 communique, the method of putting down in writing in the same 42-711 communique of passing through interfacial polymerization, No. 3418250 specification of United States Patent (USP), the method of putting down in writing in same No. 3660304 specification of passing through to separate out polymer, the method of the use isocyanates polyalcohol wall material of putting down in writing in No. 3796669 specification of United States Patent (USP), the method of the use isocyanates wall material of putting down in writing in No. 3914511 specification of United States Patent (USP), No. 4001140 specification of United States Patent (USP), same No. 4087376 specification, the use urea of putting down in writing in same No. 4089802 specification-formaldehyde system or urea-formaldehyde-resorcinol are the method that wall forms material, use melamine-formaldehyde resin of putting down in writing in No. 4025445 specification of United States Patent (USP), the method of wall materials such as hydroxylated cellulose, special public clear 36-9163 communique, the method of putting down in writing in the same 51-9079 communique of passing through the monomer in-situ polymerization, No. 930422 specification of BP, the spray drying process of putting down in writing in No. 3111407 specification of United States Patent (USP), No. 952807 specification of BP, the electrolysis of putting down in writing in same No. 967074 specification disperses cooling method, but the present invention is not limited to these.

The microcapsule wall that be fit to use in the microcapsules (b) is to contain three-dimensional bridged bond, have the material by the character of solvent expansion.From this point of view, the wall material of microcapsules is polyureas, polyurethane, polyester, Merlon, polyamide or these mixture preferably, particularly preferably is polyureas and polyurethane.In addition, in microcapsule wall, also can import the compound that contains heat reactivity functional group.

The average grain diameter of microcapsules (b) be preferably 0.01～20 μ m, more preferably 0.05～2.0 μ m, be preferably 0.10～1.0 μ m especially.If in above-mentioned scope, just can obtain good resolution ratio and ageing stability.

Microcapsules (b) both can be that capsule is an one by heat seal mutually, also can not be combined into one.Mainly be to ooze out capsule surface or the outer material of microcapsules during coating in the interior bag thing of microcapsules, perhaps immerse the material of microcapsule wall, preferably chemical reaction takes place by heat.Also can react with the low molecular compound of hydrophilic resin that adds or interpolation.In addition, in the microcapsules more than 2 kinds, by making it to have the functional group of the mutual thermal response of different functional groups respectively, microcapsules also can react to each other.

Thereby being integrated by the mutual fusion of hot microcapsules is being preferred aspect the formation image, but not necessarily.

The addition of microcapsules (b) in heat sensing layer is converted into solid constituent, is preferably 10～60wt%, 15～40wt% more preferably.If above-mentioned scope, can obtain developing on the good machine, obtain good speed and Nai Yin simultaneously.

When adding microcapsules (b) in heat sensing layer, bag thing in can dissolving adds the solvent that the wall material expands simultaneously in the microcapsules dispersant.By such solvent, the compound that contains heat reactivity functional group of bag is to the microcapsules external diffusion in can promoting.

Such solvent depends on material, wall thickness and the Nei Bao thing of microcapsules dispersant, microcapsule wall, but selects in most solvent that can be easy to sell from the market.For example under the situation of the water dispersible microcapsules that constitute by crosslinked polyureas, polyurethane, preferred alcohols, ethers, acetal, ester class, ketone, polyalcohols, amide-type, amine, fatty acid etc.

Concrete specifiable for example is, methyl alcohol, ethanol, the tert-butyl alcohol, normal propyl alcohol, oxolane, methyl lactate, ethyl lactate, methyl ethyl ketone, Glycol Monomethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol monomethyl ether, gamma-butyrolacton, N, dinethylformamide, N, the N-dimethylacetylamide, but the present invention is not limited to these.In addition, also can mix these solvents more than 2 kinds.

If also can use in micro-capsule dispersion liquid do not dissolve, but mix above-mentioned solvent then the solvent that dissolves.Addition depends on raw-material combination, but is preferably 5～95wt% of coating liquid usually, and more preferably 10～90wt% is preferably 15～85wt% especially.

As recording layer, contain in use and above-mentionedly to have the particulate polymer (a) of heat reactivity functional group or comprise under the situation of heat sensing layer of microcapsules (b), also can add these initiations as required or promote the compound of reaction with heat reactivity functional compounds.As the compound that causes or promote reaction, specifiable is for example to produce free radical or cationic compound by heat.Concrete specifiable be for example triphen imidazole dimer, trihalomethyl group compound, peroxide, azo-compound, comprise father-in-law's salt, acylphosphanes, imino group sulfonate such as diazol or diphenyl iodonium salt.

These compounds preferably add in 1～20wt% of heat sensing layer solid constituent scope, more preferably in the scope of 3～10wt%.If in above-mentioned scope, can the infringement machine on developing, can obtain good reaction and cause effect or reaction facilitation effect.

Also can add hydrophilic resin in the heat sensing layer.By add hydrophilic resin not only on the machine developing become well, and improved the film strength of heat sensing layer from body.

As hydrophilic resin, be preferably the resin of hydrophilic radicals such as containing hydroxyl, carboxyl, ethoxy, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl.

As the object lesson of hydrophilic resin, specifiable is Arabic gum for example, casein, gelatin, starch derivatives, carboxymethyl cellulose and sodium salt thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid class, styrene-maleic acid class, polyacrylic and salt thereof, polymethacrylic acid and salt thereof, the homopolymers of hydroxyethyl meth acrylate and copolymer, the homopolymers of hydroxy ethyl methacrylate and copolymer, the homopolymers of hydroxypropyl methyl acrylate and copolymer, the homopolymers of hydroxypropyl acrylate and copolymer, the homopolymers and the copolymer of hydroxyl butyl methyl acrylate, the homopolymers and the copolymer of hydroxyl butylacrylic acid ester, polyethylene glycols, hydroxyl acrylic polymers class, polyvinyl alcohol, degree of hydrolysis is 60wt% at least, the preferred hydrolysed polyvinyl acetate of 80wt% at least, the polyvinyl formal, the polyvinyl butyral, and PVP, the homopolymers of acrylamide and copolymer, the homopolymers of Methacrylamide and polymer, the homopolymers of N hydroxymethyl acrylamide and copolymer.

The addition of hydrophilic resin in heat sensing layer is preferably 5～40wt% of heat sensing layer solid constituent, 10～30wt% more preferably.If above-mentioned scope can obtain developing and film strength on the good machine.

In order to improve speed, on heat sensing layer, can contain the photo-thermal conversion agent that absorbs infrared ray and heating.Such photo-thermal conversion agent just can use various pigment, dyestuff and metal microparticle so long as have the light absorption material of absorption band at least a portion of 700～1200nm.

As the kind of pigment, specifiable be for example black pigment, brown pigments, red pigment, violet pigment, blue pigment, viridine green, fluorescent pigment, metal powder pigment, other polymer in conjunction with pigment.Concrete specifiable be insoluble azo colour for example, azo precipitation (the pigment of ア ゾ レ-キ), condensed azo pigment, the chelating AZOpigments, the phthalocyanine based dye, anthraquione pigmentss, dinaphthyl embedding naphthalene pigment and ペ リ ノ Application (perynon) series pigments, the thioindigo series pigments, quinacridone pigment, dioxazine pigment, isoindolone (イ ソ イ Application De リ ノ Application) series pigments, the quinophthalone series pigments, the precipitated pigment of photosensitive processing, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment, carbon black.

In the present invention, can use the pigment of selling on the market, and Colour Index (C.I.) handbook, " up-to-date pigment handbook (compile by Japanese pigment technology association, 1977 annuals), (CMC publishes " up-to-date pigment applications technology ", 1986 annuals) and the infrared absorbance pigment of record among " printing-ink technology " (CMC publish, 1984 annuals).

Pigment both can not carry out surface treatment to be used, and also can carry out surface treatment and use.As the surface-treated method, specifiable be the method for method, the adhesive surface activating agent of for example surface applied hydrophilic resin and lipophilic resin, the method for binding reactive substance (for example Ludox, alumina sol, silane coupling agent and epoxide, isocyanate compound) on surface of pigments.Above-mentioned surface treatment method is documented in " character of metallic soap alkali and application " (good fortune study), " printing-ink technology " (CMC publishes, 1984 annuals) and " up-to-date pigment applications technology " (CMC publishes, 1986 annuals).In these pigment, absorbing ultrared pigment is preferred aspect in being applicable to the laser instrument of infrared light emission.Be preferably carbon black as the ultrared pigment of such absorption.

The particle diameter of pigment is preferably in the scope of 0.01～1 μ m, more preferably in the scope of 0.01～0.5 μ m.

As dyestuff, can use the dyestuff sold on the market and, document (for example, " " near infrared absorption pigment ", 2.3 (1990) CMC of " exploitation that the nineties is functional pigmented and market trends " the 2nd chapter of dyestuff handbook (Synthetic Organic Chemistry association compiles, clear and 45 annuals), " chemical industry " in May, 1986 number the 45th～51) or patent in the known dyestuff put down in writing.

Concrete infrared ray absorbing dyestuffs such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dye, phthalocyanine dye, carbon father-in-law dyestuff, quinoneimine dye, polymethin dye, cyanine dye preferably.

In addition, specifiable is that for example the spy opens clear 58-125246 communique, same 59-84356 communique, the cyanine dye of putting down in writing in the same 60-78787 grade, the spy opens clear 58-173696 communique, same 58-181690 communique, the methine dyes of putting down in writing in the same 58-194595 grade, the spy opens clear 58-112793 communique, same 58-224793 communique, same 59-48187 communique, same 59-73996 communique, same 60-52940 communique, the naphthoquinone dyestuff of putting down in writing in the same 60-63744 grade, the spy opens ス Network ワ リ リ ウ system (squarilium) dyestuff of putting down in writing in the clear 58-112792 grade, the cyanine dye of putting down in writing in No. 434875 specification of BP, the dyestuff of putting down in writing in No. 4756993 specification of United States Patent (USP), the cyanine dye of putting down in writing in No. 4973572 specifications of United States Patent (USP), the dyestuff of putting down in writing in the Te Kaiping 10-268512 communique, the phthalocyanine compound of putting down in writing in the same 11-235883 communique.

In addition, also be fit to use as the near infrared absorption sensitive agent of putting down in writing in No. 5156938 specification of dyestuff United States Patent (USP), aryl benzo (sulfo-) the pyrene salt of the replacement of putting down in writing in No. 3881924 specification of United States Patent (USP) in addition, the spy opens the cyclonite thiapyran father-in-law salt of record in clear 57-142645 number, the spy opens clear 58-181051 communique, same 58-220143 communique, same 59-41363 communique, same No. 5984248 communiques, same 59-84249 communique, same 59-146063 communique, the pyrene based compound of putting down in writing in the same 59-146061 communique, the spy opens the cyanine dye of putting down in writing in the clear 59-216146 communique, five methine thiapyran father-in-law salt of putting down in writing in No. 4283475 specification of United States Patent (USP) etc. and the fair 5-13514 communique of spy, the pyrene compound of putting down in writing in the same 5-19702 communique suffers (the エ Port ラ イ ト) III-178 that cuts open that suffers that cuts open the manufacturing of woods (エ Port リ Application) company, suffer (the エ Port ラ イ ト) III-130 that cuts open, suffer also suitable uses of cuing open such as (エ Port ラ イ ト) III-125.

In the middle of these, preferred dyestuff is a water-soluble dye.Represent concrete example below.

Change 2 and change 3

[changing 2]

[changing 3]

Photo-thermal conversion agent as using with the oil loving compound that contains heat reactivity functional group of heat sensing layer microcapsules also can use above-mentioned infrared ray absorbing dyestuff, but more preferably uses oil loving dyestuff.As object lesson, can enumerate following cyanine dye.

(P55 changes 4)

[changing 4]

The photo-thermal conversion agent of above-mentioned organic class preferably is added in the heat sensing layer with the scope that reaches 30wt%.5～25wt% more preferably, preferred especially 7～20wt%.If in above-mentioned scope, can obtain good speed.

In heat sensing layer, also can use metal microparticle as the photo-thermal conversion agent.The metal microparticle majority has the photo-thermal transformational and has spontaneous hot.As preferred metal microparticle, specifiable is simple substance or the alloy of for example Si, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ag, Au, Pt, Pd, Rh, In, Sn, W, Te, Pb, Ge, Re, Sb, the perhaps particulate of these oxides or sulfide.

Preferred metal in the metal that constitutes these metal microparticles, be when illumination is penetrated, easily form by thermal capacitance be integrated, fusing point is about below 1000 ℃ and the metal of absorption, for example Re, Sb, Te, Au, Ag, Cu, Ge, Pb, Sn arranged in infrared, visible light or ultraviolet range.

In addition, particularly preferably be lower, the ultrared relatively absorbance of fusing point again than higher metal microparticle, for example Ag, Au, Cu, Sb, Ge, Pb, as most preferred element, specifiable is Ag, Au, Cu.

In addition, can mix the particulate of spontaneous hot metals such as the particulate that uses low-melting-point metals such as Re, Sb, Te, Au, Ag, Cu, Ge, Pb, Sn for example and Ti, Cr, Fe, Co, Ni, W, Ge, also can constitute with the photo-thermal conversion material more than 2 kinds.In addition when making small of AgPtPd etc. combined light to absorb small of king-sized metal kind and small use of other metals also be preferred.

The particle diameter of these particles is preferably below the 10 μ m, and following is 0.003～5 μ m, is preferably 0.01～3 μ m especially.If in above-mentioned scope, can obtain good speed and resolving power.

In the present invention, when using these metal microparticles as the photo-thermal conversion agent, its addition is preferably the 10wt% of heat sensing layer solid constituent, more preferably more than the 20wt%, is preferably more than the 30wt% especially.If in above-mentioned scope, can obtain higher speed.

The adjoining course of heat sensing layer is also can contain the photo-thermal conversion agent in priming coat and the water-soluble external coating described below.By making that at least one layer contains the photo-thermal conversion agent in heat sensing layer, priming coat and the external coating, can improve ultrared absorption efficiency, improve speed.

In addition as required, can also add all cpds except that above-mentioned in the heat sensing layer.For example, in order further to improve anti-brush power, can in the heat sensing layer matrix, add polyfunctional monomer.As this polyfunctional monomer, can use as the monomer that monomer exemplified that adds in the microcapsules.As particularly preferred monomer, can enumerate trimethylolpropane triacrylate.

In addition, in order in heat sensing layer, after forming image, to be easy to generate the difference of image section and non-image part, can to use the dyestuff that has bigger absorption in the visible region colouring agent as image.Concrete specifiablely be that oil yellow #101, oil yellow 103, oil-bound distemper are red 312, glossy dark green BG, oil blue BOS, oil blue #603, glossy black BY, glossy black BS, glossy black T-505 (above made by Lin Ante (オ リ エ Application ト) chemical industrial company), Victoria's ethereal blue, gentian violet (CI42555), crystal violet (CI42535), ethyl violet, rhodamine B (CI145170B), peacock green (CI42000), methylenum careuleum (CI52015), spy open the dyestuff of putting down in writing in the clear 62-293247 communique.In addition, pigment such as phthualocyanine pigment, azo pigment, titanium oxide also can be fit to use.Addition is preferably 0.01～10wt% with respect to all solids composition of heat sensing layer coating liquid.

In addition, in the present invention,, preferably add a spot of thermal polymerization inhibitor in order to stop the unwanted thermal polymerization of ethene unsaturated compound in the modulation neutralization of heat sensing layer coating liquid is preserved.As the thermal polymerization inhibitor that is fit to, specifiable is for example quinhydrones, p methoxy phenol, BHT, benzenetriol, tert-butyl catechol, benzoquinones, 4,4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), N-nitroso-N-hydroxyanilines aluminium salt.The addition of thermal polymerization inhibitor is preferably the about 0.01～5wt% with respect to total composition weight.

In addition as required, because the polymerization that oxygen produces hinders, also can add in the higher fatty acids of behenic acid and behenic acid acid amides and so on and derivative thereof, the dry run after coating being prevalent on the surface of heat sensing layer in order to prevent.The addition of higher fatty acids and derivative thereof is preferably about 0.1～about 10wt% of heat sensing layer solid constituent.

In addition, in heat sensing layer, can add the plasticizer that is used to give coating flexibility etc. as required.As plasticizer, specifiable is for example polyethylene glycol, ATBC, diethyl phthalate, dibutyl phthalate, DHP, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate.

Heat sensing layer is essential above-mentioned each composition to be dissolved in be modulated into coating liquid in the solvent, then coating.As solvent used herein, specifiable is for example dichloroethylene, cyclohexanone, methyl ethyl ketone, methyl alcohol, ethanol, propyl alcohol, ethylene glycol-methyl ether, 1-methoxyl group-2-propyl alcohol, 2-methoxy ethyl acetal, 1-methoxyl group-2-propyl group acetal, dimethoxy-ethane, methyl lactate, ethyl lactate, N, N-dimethylacetylamide, N, dinethylformamide, tetramethylurea, N-methyl pyrrolidone, methyl-sulfoxide, sulfolane, gamma-butyrolacton, toluene, water, but be not limited thereto.These solvents can be used alone or as a mixture.The solid component concentration of coating liquid is preferably 1～50wt%.

In addition, the heat sensing layer coating amount (solid constituent) after coating and the drying on the supporter that obtains is according to purposes and difference still generally is preferably 0.5～5.0g/m ²If coating amount lacks than above-mentioned scope, it is big that apparent speed becomes, but the film characteristics of finishing the heat sensing layer of image writing function reduces.Method as coating can make in all sorts of ways.Specifiablely be that for example rod is coated with, spin coating, spraying, the coating of curtain membrane type, dip-coating, air-blade type coating, blade type coating, roller coating.

In the coating liquid of heat sensing layer, can adding the surfactant that is used for improving screening characteristics, for example special to open the fluorine that clear 62-170950 communique puts down in writing be surfactant.Addition is preferably 0.01～1wt% of heat sensing layer solid constituent, more preferably 0.05～0.5wt%.

In original edition of lithographic printing plate of the present invention, in order to prevent because the pollution on the lipophilicity substance heat sensing layer surface of causing can be provided with water miscible external coating on heat sensing layer.The water-soluble external coating that uses among the present invention is the coating that can be easy to remove when printing, contains the resin that is selected from water miscible organic high molecular compound.

As water miscible organic high molecular compound, specifiable is can be by applying drying, filming and contain the material that film forms energy.What specifically can exemplify is polyvinyl acetate (wherein percent hydrolysis is the material more than 65%); Polyacrylic acid, its alkali metal salt or amine salt; Acrylic copolymer, its alkali metal salt or amine salt; Polymethylacrylic acid, its alkali metal salt or amine salt; Polymethyl acid copolymer, its alkali metal salt or amine salt; Polyacrylamide, its copolymer; The poly-hydroxyethyl acrylate; PVP, its copolymer; Polyvinyl methyl ether; Vinyl methyl ether/copolymer-maleic anhydride; Poly--2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid, its alkali metal salt or amine salt; Poly--2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid copolymer, its alkali metal salt or amine salt; Arabic gum; Cellulose derivative (for example carboxymethyl cellulose, carboxyethyl cellulose, methylcellulose), its sex change body; White dextrin; Furans (プ Le ラ Application); Fermentation etherificate dextrin.In addition, according to purpose, can mix these materials uses more than 2 kinds.

In addition, on external coating, also can add above-mentioned photo-thermal conversion agent.

Pigment as the photo-thermal conversion agent uses in order to improve with respect to the dispersiveness of adding layer, can to carry out known surface treatment as required and use.As the surface-treated method, can enumerate said method.

Be added into the pigment of external coating, preferably surperficial with water-soluble resin and the easy pigment that disperses and do not damage hydrophilic hydrophilic resin and Ludox coating.As the method for dispersed color, can use the known dispersion technology that can be used in printing ink manufacturing, the toner manufacturing etc.

As particularly preferred pigment, specifiable is carbon black.

Using pigment system and dyestuff is under the situation of photo-thermal conversion agent, and its adding proportion is preferably 1～70wt% of external coating solid constituent, more preferably 2～50wt%.

If in above-mentioned scope, can obtain good speed, but in external coating, add under the situation of photo-thermal conversion agent, according to its addition, can reduce the addition of the photo-thermal conversion agent of heat sensing layer and priming coat sometimes, do not add sometimes.

In addition, in order to ensure the uniformity that applies in the external coating, in aqueous solution coating, can add nonionics such as polyoxyethylene nonylplenyl ether, polyoxyethylene lauryl ether is surfactant.

The drying coated amount of external coating is preferably 0.1～2.0g/m ²Development property on the not infringement machine in this scope, the lipophilicity substances such as spot by fingerprint adhesion can prevent the pollution on heat sensing layer surface well.

In original edition of lithographic printing plate of the present invention, also can use except above-mentioned containing (a) as recording layer to have the particulate polymer of heat reactivity functional group or (b) to comprise recording layer the heat sensing layer of microcapsules with heat reactivity functional compounds.Specifiable is photosensitive layer, the photosensitive layer that uses eurymeric infrared laser recording materials that for example uses minus infrared laser recording materials, the photosensitive layer that uses sulfonate type infrared laser material.

Under the situation of the minus lithographic plate that manufacturing original edition of lithographic printing plate of the present invention can expose in infrared laser, so-called hot negative-type original edition of lithographic printing plate, preferably use minus infrared laser recording materials that photosensitive layer is set.

As minus infrared laser recording materials, be fit to use the compound of representing by sour crosslinked crosslinking agent, (C) alkali soluble resin, (D) infrared absorbent and (E) general formula (R3-X) n-Ar-(OH) m by light or thermal decomposition and acidic compound, (B) by (A) (in the formula, R3 represents that carbon number is 6～32 alkyl or alkenyl, X represents singly-bound, O, S, COO or CONH, Ar represents aromatic hydrocarbyl, aliphatic alkyl or heterocyclic group, n represents 1～3 integer, and m represents 1～3 integer.) composition formed.

In general, there is the defective that what is called fingerprint after development adheres to easily, the intensity of image section weakens in hot negative-type original edition of lithographic printing plate, and eliminates but such defective can form photosensitive layer by above-mentioned composition.

Pass through light or the acidic compound of thermal decomposition as (A), specifiable is to represent special be willing to the imino group sulfonate of record in the flat 3-140109 specification (spy opens flat 04-365048 communique), the compound that the light decomposition produces sulfonic acid, and specifiable again is by the irradiation of 200～500nm wavelength or the acidic compound of the heating more than the 100C.

As suitable acid producing agent, specifiable is initator, the light decolorizer of pigment, the phototropic agent of for example light cationic polymerization initiators, optical free radical polymerization.These acid producing agents preferably add with the amount with respect to recording materials total solids content 0.01～50wt%.

As (B) by the crosslinked crosslinking agent of acid, be fit to enumerate be for example (i) aromatic compound of replacing with alkoxy methyl or hydroxyl, (ii) contain the compound of N-hydroxymethyl, N-alkoxy methyl or N-acyl group oxygen methyl, (iii) epoxide.

As (C) alkali soluble resin, specifiable is the polymer that for example contains hydroxyaryl on phenolic resins and the side chain.

As (D) infrared absorbent, specifiable is for example effectively to absorb the dyestuff of selling on the markets such as the ultrared azo dyes of 760～1200nm, anthraquinone dye, phthalocyanine dye; The black pigment of putting down in writing in the Colour Index, red pigment, metal powder pigment, phthualocyanine pigment.In addition, in order to improve the Yi Jianxing of image, preferably add image colouring agents such as oil yellow, oil blue #603.In addition, in order to improve the flexibility that photosensitive layer is filmed, can add the plasticizer of polyethylene glycol and phthalic acid ester and so on.

In addition, under the situation of the eurymeric lithographic plate that manufacturing original edition of lithographic printing plate of the present invention can expose in infrared laser, so-called hot positive type original edition of lithographic printing plate, preferably use eurymeric infrared laser recording materials that photosensitive layer is set.

As eurymeric infrared laser recording materials, be fit to use by (A) alkali-soluble macromolecule, (B) and dissolve each other with this alkali-soluble macromolecule and make compound that the alkali dissolubility reduces and (C) absorb the eurymeric infrared laser recording materials that the compound of infrared laser is formed.

If use this eurymeric infrared laser recording materials, non-image part can be eliminated with respect to alkaline-based developer dissolubility deficiency, the original edition of lithographic printing plate that alkali resistance development adaptability aspect is good, picture steadiness is good that is difficult to breakage, image section can be made in addition.

As the alkali-soluble macromolecule, specifiable be the macromolecular compound that contains the phenol hydroxyl of for example representatives such as (i) phenolic resin, cresol resin, phenolic resins, benzenetriol resin, (ii) make the molecule contain the independent polymerization of polymerization single polymerization monomer of sulfuryl amine group or the compound that obtains with other polymerizable monomer copolymerization, (iii) representative such as N-(p-toluenesulfonyl) Methacrylamide, N-(p-toluenesulfonyl) acrylamide contain the compound of active imino group.

Dissolve each other and make the compound that the alkali dissolubility reduces as (B) and above-mentioned (A) composition, specifiable is the compound of sulphones, ammonium salt, sulfonium salt, amide compound etc. and above-mentioned (A) interaction between component for example.Be under the situation of phenolic resins at above-mentioned (A) composition for example, what be fit to enumerate as (B) composition is anthocyanidin.

Absorb the compound of infrared laser as (C), preferably absorption band is arranged, have light/material of hot translation function at 750～1200nm region of ultra-red.As having such materials with function, specifiable be for example be Ku Wa inner room wood (ス Network ワ リ リ ウ system) pigment, pounce on inner room wood (ピ リ リ ウ system) salt pigment, carbon black, azoic dyes insoluble azo dyes, anthraquinone based dye.These are preferably the size of 0.01～10 mu m range.

Hot positive type original edition of lithographic printing plate can make as follows: these eurymeric infrared laser recording materials are dissolved in the organic solvents such as methyl alcohol, methyl ethyl ketone, add dyestuff as required, coating and drying make that dried weight is 1～3g/m on supporter ²

In addition, in original edition of lithographic printing plate of the present invention, also can use sulfonate type infrared laser recording materials as recording layer.

As sulfonate type infrared laser recording materials, can use for example sulfonate compound of middle record such as No. 270480 specification of patent, No. 2704872 specification of patent.Also can use heat to produce sulfonic acid, water-soluble photosensitive material in addition by producing by the infrared laser irradiation, with collosol and gel fixedly styrene sulfonate, shine photosensitive material that the infrared laser surface polarity changes and specially be willing to flat 9-89816 specification (spy opens flat 10-282646 communique), specially be willing to flat 10-22406 specification (spy opens flat 11-218928 communique), specially be willing to that the laser explosure hydrophobic surface that passes through of record in the flat 10-027655 specification (spy opens flat 10-282672 communique) changes to hydrophilic photosensitive material then.

In addition, produce the characteristic of the photosensitive layer that sulfonic macromolecular compound forms, the method that the preferred combination use is enumerated below in order further to improve by heat by this.As such method, specifiable is that for example (1) spy is willing to the middle method of passing through to be used in combination acid or alkali propellant put down in writing of flat 10-7062 specification (spy opens flat 11-202483 communique), (2) the special method that specific intermediate layer is set of being willing to record in the flat 9-340358 specification (spy opens flat 11-174685 communique), (3) the special method that is used in combination specific crosslinking agent of being willing to record in the flat 9-248994 specification (spy opens flat 11-84658 communique), (4) special method of being willing to that the form with the solid particle surfaces modification of record is used in the flat 10-115354 specification (spy opens flat 11-301131 communique).

In addition, as utilizing the heat that produces by laser explosure to change other examples of the parent/hydrophobic composition of photosensitive layer, specifiable is that the heat of for example putting down in writing in No. 2764085 specification of United States Patent (USP) of being made up of the Werner complex compound of passing through changes to hydrophobic composition, the certain sugars of putting down in writing in the special public clear 46-27219 communique, melamino-formaldehyde resins etc. change to hydrophilic composition by exposure, the spy opens the mode of heating exposure of putting down in writing in the clear 51-63704 communique of passing through and changes to hydrophobic composition, put down in writing in No. 4081572 specification of United States Patent (USP) by the composition of as phthalylhydrazine, forming by the polymer of thermal dehydration/hydrophobization, that puts down in writing in the special fair 3-58100 communique has tetrazolium father-in-law salt structure and passes through to heat the composition of hydrophiling, the spy open put down in writing in the clear 60-132760 communique by the sulfonic acid modified polymer form pass through the exposure hydrophobization composition, the spy open put down in writing in the clear 64-3543 communique by the imino group precursor polymer form pass through the exposure hydrophobization composition, the spy opens the composition of putting down in writing in the clear 51-74706 communique of being made up of the fluorocarbons polymer that passes through the exposure hydrophiling, can use these compositions to form recording layer.

In addition, the specifiable spy of being opens the exposure of putting down in writing in the flat 3-197190 communique of being made up of the hydrophobicity crystalline polymer of passing through and changes to hydrophilic composition, put down in writing in the Te Kaiping 7-186562 communique by changing to the composition that hydrophilic polymers and photo-thermal conversion agent are formed by heating infusible side group, the composition that passes through the exposure hydrophobization that the three-dimensional cross-linked hydrophilic adhesive of putting down in writing in the Te Kaiping 7-1849 communique by containing microcapsules is formed, valence isomerization or the proton put down in writing in the Te Kaiping 8-3463 communique move isomerized composition, the phase structure of putting down in writing in the Te Kaiping 8-141819 communique of passing through in the heating genetic horizon changes (fusing mutually), change parent/hydrophobic composition, that puts down in writing in the special public clear 60-228 communique passes through area of heating surface form, the composition that the parent on surface/hydrophobicity changes can use these compositions to form recording layer.

In the present invention, as other examples of the preferred recording materials that are used for recording layer, specifiable is to utilize the heat that produced by high power and highdensity laser, so-calledly change close-burning composition between photosensitive layer and the supporter by the mode of heating exposure.Concrete specifiable be the composition of putting down in writing in the special public clear 44-22957 communique of forming by thermal viscosity material or heat reactivity material.

The original edition of lithographic printing plate of the present invention that so obtains is characterized in that on the cutting plane of the anodic oxidation film after above-mentioned recording layer is set, and is below 1.0 with the carbon of following formula (1) expression and the atomicity of aluminium than (C/Al).

C/Al＝(Ic/Sc)/(Ial/Sal) (1)

Ic: the auger electrons derivative-type peak of carbon (KLL) is to peak intensity

Ial: the auger electrons derivative-type peak of aluminium (KLL) is to peak intensity

Sc: the relative sensitivity coefficient of the auger electrons of carbon (KLL)

Sal: the relative sensitivity coefficient of the auger electrons of aluminium (KLL)

For the atomicity of carbon and aluminium computational methods, adopt accompanying drawing to be described more specifically than (C/Al).

Fig. 1 is that the cutting plane for the anodic oxidation film of original edition of lithographic printing plate carries out the illustration intention that the auger electrons spectrum analysis obtains.Among Fig. 1, C is the peak of carbon, and Al is the peak of aluminium, and O is the peak of oxygen.The auger electrons spectrum analysis can carry out as follows: with original edition of lithographic printing plate bending 180 ℃ of cutting planes of making anodic oxidation film almost, be fixed on the attached specimen holder of auger electrons spectroscopy apparatus, in the gatherer before be about to analyzing.

Can obtain Ic (the auger electrons derivative-type peak of carbon (KLL) is to peak intensity) and Ial (the auger electrons derivative-type peak of aluminium (KLL) is to peak intensity) from Fig. 1.Sc (the relative sensitivity coefficient of the auger electrons of carbon (KLL)) value is 0.076, and Sal (the relative sensitivity coefficient of the auger electrons of aluminium (KLL)) value is 0.105, in the Ic and the above-mentioned formula of Ial value substitution (1) that will obtain, calculates C/Al.In Fig. 1, C/Al=0.76.

Also have, C/Al preferably adopts a plurality of points (for example 5 points) of the cutting plane of anodic oxidation film to carry out the auger electrons spectrum analysis, obtains its mean value.

The condition of below representing a routine auger electrons spectrum analysis.

Measure machine: FE-AES type SMART-200, A Lu sends out second (ア Le バ Star Network Off ア イ) company in half short storehouse and makes

Irradiation electric current: about 10nA

Accelerating potential: 10kV

Irradiating electron beam footpath: focus on

Chamber inner pressure: about 1 * 10 ^-10Torr (about 1.33 * 10 ^-8Pa)

Detection range: 20～2020eV, 0eV/step, 20ms/step

Amplifier voltage: 2250V

In the present invention, C/Al below 1.0, is preferably below 0.8 on the cutting plane of the anodic oxidation film after recording layer is set.C/Al is below 1.0, by suppressing to invade in the micropore of anodic oxidation film, can keep the pyroconductivity that the anodic oxidation film behind the recording layer is set than the lowland, anti-seal, speed and the spot-resistant of original edition of lithographic printing plate of the present invention thus when making lithographic plate all becomes good.

Below, describe at the manufacturing installation of the aluminium support body that uses among the present invention.

Manufacture process as the aluminium support body that uses among the present invention, be preferably (1) with rolling, being wound into spiral helicine aluminium sheet exports from the let-off motion of being made up of the multiaxis capstan head, (2) (surface coarsening of machinery is handled in above-mentioned each processing, electrochemical surface coarsening is handled, alkaline corrosion is handled, sour corrosion is handled, go spot to handle, anodized, (acid treatment or alkali treatment) handled in reaming, sealing of hole is handled, hydrophilic surface processing etc.) afterwards, the dry aluminium sheet of handling, (3) aluminium sheet is wound into helical form in the above-mentioned coiler device of being made of the multiaxis capstan head, perhaps correct the flatness of aluminium sheet, cut into the length of regulation then and gather.In addition, as required, in said process, also can be provided with and form priming coat and recording layer and the dry operation of handling, original edition of lithographic printing plate is wound into helical form by above-mentioned coiler device.

In addition, in the manufacturing of aluminium support body, preferably has more than 1 the operation of using this defective of device continuous review of checking the surface of aluminum plate defective, pasting target labels in the marginal portion of the defective aluminium sheet of finding.In addition, in the manufacturing of original edition of lithographic printing plate of the present invention, preferably be arranged in aluminium sheet output operation and the coiling operation, even in the exchange of aluminium coiled material, stop to move of this aluminium sheet, also can remain on the constant stand-by provision of translational speed of aluminium sheet in above-mentioned each operation, after above-mentioned aluminium coiled material output operation, the joint operation of ultrasonic wave or arc welding aluminium sheet is set preferably.

The device that uses during aluminium support body is made, preferably have and measure the shift position of aluminium sheet more than 1 and correct the device of shift position, in addition, preferably has the tension-adjusting gear that is used to control the drive unit of aluminium sheet tension force reduction (カ Star ト) and translational speed more than 1 and is used to control tension force respectively.

In addition, also whether the state that preferably writes down each operation with tracking means is the condition of wishing, before the aluminium coiled material is reeled, at the marginal portion adhesive label of aluminium web (ウ エ Block), can judge whether be the condition of wishing behind its label.

In the present invention, preferably make aluminium sheet, cut and/or be divided into the length of regulation then with closing the charged and mutual absorption of paper.In addition,, being cut into specific length after or before the cutting, serving as a mark with its label and to distinguish certified products partly and the substandard products part, only collect the certified products part preferably according to the information of the label of pasting in the aluminium sheet marginal portion.

In containing each operation such as above-mentioned output operation, according to the size (thickness and width) of aluminium sheet, the material of aluminium and the translational speed of aluminium web, it is important setting best tension force under condition separately.Therefore, the tension-adjusting gear that preferably is used to control the drive unit of tension force reduction and translational speed and is used to control tension force is provided with the tenslator of a plurality of FEEDBACK CONTROL from the tension sensing device signal.Drive unit generally uses the control method of combination d.c. motor and main head roll.Main head roll with general natural gum as material, but the cylinder that the aluminium web can use the laminated nonwoven fabric to make in the operation of wet (wet) state.In addition, as each passage roller (パ ス ロ-ラ), generally can use natural gum or metal, but in aluminium web and the place that is easy to generate slip for anti-sliding stop, each passage roller (also can be provided with on the パ ス ロ-ラ) connect motor and reductor, by from the signal of main drive with constant auxiliary drive units such as speed rotation control.

The aluminium support body that uses among the present invention, as the spy open put down in writing in the flat 10-114046 communique, at arithmetic average roughness (R with rolling direction _a) as R ₁, with the arithmetic average roughness (R of cross direction _a) as R ₂Situation under, R ₁-R ₂Preferably at R ₁30% in, preferably the average curvature of rolling direction is 1.5 * 10 in addition ^-3Mm ^-1Below, the average curvature of cross direction is 1.5 * 10 ^-3Mm ^-1Below, the average curvature of rolling direction and vertical direction is 1.0 * 10 ^-3Mm ^-1Below.

In addition, carry out the aluminium support body of manufacturings such as above-mentioned surface coarsening processing, preferably using diameter of cylinder is that 20～80mm, gummy hardness are the rectification cylinders rectification of 50～95 degree.Thus, even in the automatic transmission operation of lithographic plate sensitization printing machine, also can supply with the spiral helicine roughing thin plate of aluminium of the flatness that can not produce original edition of lithographic printing plate exposure skew.Open in the flat 9-194093 communique the spy, put down in writing the curling assay method and the device of web, curl bearing calibration and device and web shearing device, also can use these among the present invention.

In addition, when continuous manufacturing aluminium support body, under suitable condition whether each operation of pyroelectric monitor operation, whether the state that writes down each operation with tracking means is the condition of wishing, before the aluminium coiled material is reeled, at the marginal portion of aluminium web adhesive label, can judge whether it is the condition of wishing by its label afterwards, when cutting, collection, can judge whether its part is qualified.

The treating apparatus of the aluminium sheet that in above-mentioned surface coarsening is handled, uses, preferably measure in fluid temperature, proportion, electrical conductivity, the hyperacoustic spread speed more than one, obtain the composition of liquid, and carry out FEEDBACK CONTROL, and/or the constant device of FEEDFORWARD CONTROL control strength of fluid.

In the acidic aqueous solution in above-mentioned treating apparatus, begin to dissolve for the composition that contains in the aluminum ions aluminium sheet is accompanied by the carrying out that surface of aluminum plate handles.Therefore, in order to keep the constant concentration of aluminium ion concentration and acid or alkali, preferred gap ground adds water and acid or water and alkali and keeps liquid to form constant.Here the concentration of acid of Tian Jiaing or alkali is preferably 10～98wt%.

In the concentration of above-mentioned acid of control or alkali, preference such as following method.

Measuring conductance, proportion or hyperacoustic spread speed of each composition solution in the concentration range of being scheduled to use at each temperature and making tables of data at every turn at first, in advance.Measure concentration with reference to the tables of data of the determined liquid of conductance, proportion or the hyperacoustic spread speed and the temperature data of making determined liquid in advance then.The method in above-mentioned hyperacoustic propagation time is measured on high accuracy, high stable ground, is documented in the spy and opens in the flat 6-235721 communique.In addition, measure the system of concentration for utilizing above-mentioned hyperacoustic spread speed, being documented in the spy opens in the clear 58-77656 communique, in addition, make in advance expression relate to each liquid component a plurality of physical quantity data tables of data and measure the method for the concentration of multicomponent liquid with reference to this tables of data, be documented in the spy and open in the flat 4-19559 communique.

If the method for measurement of concentration that will adopt above-mentioned ultrasonic propagation velocity is in conjunction with the conductance and the temperature value of determined liquid and be applied in the surface coarsening operation of aluminium support body, because the management of accurately operating in real time, will make the goods of constant-quality, involve the raising of productive rate.In addition, if will be not only in conjunction with temperature, hyperacoustic spread speed and conductance, and serviceability temperature and physical quantity separately such as proportion, temperature and conductance, temperature and conductance and proportion etc. make in advance for the tables of data of each concentration and temperature and with reference to the method that this tables of data is measured the concentration of multicomponent liquid and being applied in the surface coarsening treatment process of aluminium support body, can obtain and above-mentioned same effect.

In addition, by obtain the concentration of slurry of determinand with reference to the tables of data of measuring proportion and temperature, make in advance, also can be rapidly and carry out the mensuration of concentration of slurry exactly.

Because the mensuration of above-mentioned ultrasonic propagation velocity is subjected to influence of air bubbles in the solution easily, therefore more preferably arranged perpendicular and from below carry out certain pipeline of flowing upward.The mensuration of above-mentioned ultrasonic propagation velocity, preferably the pressure in pipeline is 1～10kg/cm ²Pressure limit in carry out, frequency of ultrasonic is preferably 0.5～3MHz.

In addition, because the mensuration of above-mentioned proportion, conductance, ultrasonic propagation velocity is subjected to Temperature Influence easily, therefore preferably is being in keeping warm mode and temperature change and is being controlled at ± 0.3 ℃ measure in interior pipeline.In addition, because conductance and hyperacoustic spread speed preferably measure under uniform temp, therefore particularly preferably in mensuration in the identical pipeline and in the identical pipeline liquid stream.Because it is the pressure oscillation when measuring involves the change of temperature, therefore preferably low as far as possible.In addition, the velocity flow profile in the pipeline of mensuration is also preferably few as much as possible.In addition, because said determination is subjected to slurries, waste residue and influence of air bubbles easily, the preferred solution of measuring by filter and degasser etc.

The original edition of lithographic printing plate of the present invention that makes thus is by adding the thermosetting image.Specifically, by the first-class through image sample record of heat record, by infrared laser scan exposure, adding can the contour illumination flash exposure of flash lamp, be fit to by the high power red outside line laser explosure of the solid of infrared lamp.

At original edition of lithographic printing plate of the present invention is to contain (a) to have the particulate polymer of heat reactivity functional group or (b) comprise under the situation of developable heat sensing layer on the microcapsules with heat reactivity functional compounds, the so-called machine, can after image exposure, not have above processing and be loaded on the printing machine, use printing ink and/or dumping processing solution according to common order printing.In addition, as putting down in writing in No. 2938398 specification of patent, on being installed in cylinders of printing press after, by being loaded in the laser explosure on the printing machine, coat printing ink and/or dumping processing solution then, also can develop on the machine.In these cases, owing to remove heat sensing layer, do not need other developing procedures, in addition after developing, do not need to stop the printing machine that to be used to print, can proceed printing immediately after finishing developing by printing ink on the printing machine and/or damping water.

Promptly, the making sheet of former lithographic printing plate of the present invention and printing process, the original edition of lithographic printing plate that it is characterized in that being provided with developable heat sensing layer on the machine carries out image exposure by laser and is directly installed on the printing machine then and prints, and carries out image exposure directly printing then by laser after perhaps being installed on the printing machine.As laser, can use radiation ultrared Solid State Laser of 760～1200nm or semiconductor laser.

Also have, though contain organic in the situation of developable heat sensing layer, also can be used for printing making after the water or the suitable aqueous solution develops as developer solution.

In addition, contain at original edition of lithographic printing plate of the present invention under the situation of existing hot positive type or hot negative-type recording layer, can after image exposure,, be loaded on the printing machine, supply in printing according to usual way by developing liquid developing.

For each detailed content of handling of above-mentioned every middle record, the known condition of suitable employing.In addition, the content quotation of the document of enumerating in this specification and as the content of this specification.

The specific embodiment

The embodiment that enumerates below is just in order to specify the present invention, and the present invention is not limited to these.

1-1. the manufacturing of aluminium support body

(Production Example 1 of supporter)

The aluminium sheet that from the Al-alloy metal solution of the alloying component that contains the composition A shown in the table 1, is adopted in making embodiments of the invention as described below and the comparative example.

At first, in Al-alloy metal solution, carry out handling, make the ingot bar of thick 500mm by the DC casting by the metallic solution that the degassing and filtration constitute.After the ingot bar surface that obtains was cut into the plane of 10mm, the heating ingot bar not carrying out beginning hot rolling under the situation that evenly heating handles under 400 ℃ temperature, was rolling to till the thickness of slab 4mm.Then, be cold-rolled to thick 1.5mm, carry out the centre burn blunt after, cold rolling once more, rebuild to behind the 0.24mm, correct through flatness, obtain aluminium sheet.

Table 1

Form	Fe (Wt ％)	Si (Wt ％)	Cu (Wt ％)	Ti (Wt ％)	Mn (Wt ％)	Mg (Wt ％)	Zn (Wt ％)	Cr (Wt ％)	Other (Wt %)	Al (Wt％ )
											A	0.31	0.06	0.01	0.03	0.01	0.01	0.0	0.01	0.01	99.55

Aluminium sheet to the composition A that obtains carries out carrying out surface treatment according to the order of (1) that shows down～(9).In addition, after each surface treatment and washing, carry out water squeezing with roll.Washing will be sprayed water from nozzle.

(1) surface coarsening of machinery is handled

With proportion be the suspension of 1.12 silica sand (grinding agent, average grain diameter are 25 μ m) and water as grinding milk, on one side supply with to surface of aluminum plate by jet pipe, the surface coarsening that carries out machinery with the brush roll of the nylon bruss that has rotation is handled on one side.

The material of the nylon bruss that uses is 6, and 10-nylon, staple length are 50mm, and the diameter of hair is 0.48mm.This nylon bruss is to offer the hole in the stainless steel cylinder of φ 300mm, and the dense planting hair is made in the hole.

Brush roll uses 3 nylon brusses, and the distance that is located between 2 support roller (φ 200mm) of brush bottom is 300mm.

Load before being pressed on the aluminium sheet with respect to nylon bruss is managed the load of the CD-ROM drive motor of rotary brush, depresses above-mentioned brush roll, and making the average arithmetic roughness (Ra) of the aluminium sheet behind the surface coarsening is 0.45 μ m.The direction of rotation of brush is identical with the moving direction of aluminium sheet.After this wash.

The concentration of grinding agent is the table of comparisons that makes with reference to the relation according in advance abrasive concentration and temperature, proportion, obtains the concentration of grinding agent according to temperature and proportion, adds water and grinding agent by FEEDBACK CONTROL, makes the concentration of above-mentioned grinding agent keep constant.If, will change the surface configuration of the aluminium sheet of surface coarsening, therefore can discharge the less grinding agent of granularity successively by cyclone separator because the granularity that grinding agent is pulverized reduces.Make the particle diameter of grinding agent remain in 1～35 mu m range.

(2) alkaline corrosion is handled

The aqueous solution that contains 27wt%NaOH and 6.5% aluminum ions temperature and be 70 ℃ is ejected on the aluminium sheet by jet pipe, carries out alkaline corrosion and handles.The meltage on the surface of the electrochemical surface of the process after this roughening treatment of aluminium sheet is 8g/m ², the meltage of its inside is 2g/m ²

The concentration of the corrosive liquid that alkaline corrosion handle to adopt is with reference to the table of comparisons that makes according to the relation of the conductance of the concentration of NaOH, aluminum ions concentration, temperature, proportion, liquid in advance, obtain the concentration of corrosive liquid according to temperature, proportion and conductance, pass through FEEDBACK CONTROL, add the NaOH aqueous solution of water and 48wt%, to guarantee constant concentration.After this wash.

(3) go spot to handle

Is 35 ℃ aqueous solution of nitric acid with nozzle to the aluminium sheet injection temperation, carries out the spot that goes of 10 second time and handles.Aqueous solution of nitric acid can adopt the waste liquid that overflows from the used electrolysis unit of next operation.Set the quantity and the position of spraying the jet pipe that removes the spot treatment fluid, making can be not dry until next operation surface of aluminum plate.

(4) electrochemical surface coarsening is handled

Adopt the alternating current of trapezoidal wave shown in Figure 2 and the groove of electrolysis unit 2 shown in Figure 3 to carry out continuous electrochemical surface roughening treatment.Acidic aqueous solution adopts the aqueous solution of nitric acid (aluminium ion and the concentration that contain 0.5wt% are the ammonium ion of 0.007wt%) of 1wt%.Fluid temperature is 50 ℃.The current value of alternating current is 1msec from 0 time tp and tp ' until the peak value that reaches negative electrode cycle side and anode cycle side, and graphite electrode forms the utmost point.Current density when alternating current reaches peak value is at aluminium sheet during as anode and all be 50A/dm during negative electrode ², the electric weight (Q when electric weight during the alternating current negative electrode (Qc) and anode _A) ratio (Qc/Q _A) be 0.95, power ratio is 0.50, and frequency is 60Hz, and the summation of the electric weight during anode is 180C/dm ²After this wash with nozzle.

The control of the concentration of aqueous solution of nitric acid is nitric acid stoste and the water that adds 67wt% with the energising amount pro rata, overflows from electrolysis unit gradually with the acidic aqueous solution (aqueous solution of nitric acid) of the interpolation volume same capability of nitric acid and water, and discharges outside the electrolysis unit.Simultaneously, with reference to the table of comparisons that makes according to the relation between the ultrasonic transmission speed of the conductance of concentration of nitric acid and aluminium ion concentration, temperature, liquid, liquid in advance, obtain the concentration of this aqueous solution of nitric acid according to temperature, conductance, the ultrasonic transmission speed of aqueous solution of nitric acid, transfer gradually-addition of whole nitric acid stoste and water controls, thus guarantee constant concentration.

(5) alkaline corrosion is handled

Spraying the temperature contain NaOH26wt% and aluminium ion 6.5wt% with nozzle to aluminium sheet is 45 ℃ the aqueous solution, carries out alkaline corrosion and handles.The meltage of aluminium sheet is 1g/m ²The concentration of corrosive liquid is with reference to the table of comparisons that makes according to the relation between the conductance of the concentration of NaOH and aluminum ions concentration, temperature, proportion, liquid in advance, obtain the concentration of corrosive liquid according to temperature, proportion and conductance, pass through FEEDBACK CONTROL, add the NaOH aqueous solution of water and 48wt%, to guarantee constant concentration.After this wash.

(6) sour corrosion is handled

As acid etching solution, under 80 ℃ condition, sprayed sulfuric acid 8 seconds to aluminium sheet with sulfuric acid (sulfuric acid concentration is 300g/L, and aluminum ions concentration is 15g/L), carry out sour corrosion and handle from jet pipe.With reference to the table of comparisons that makes according to the relation of sulfuric acid concentration and aluminium ion concentration, temperature, proportion and liquid conduction rate in advance, obtain the concentration of acid etching solution according to temperature, proportion and conductance, pass through FEEDBACK CONTROL, add the sulfuric acid of water and 50wt%, make the concentration of acid etching solution keep constant.After this, wash.

(7) anodized

Adopt concentration of nitric acid be the aqueous solution (aluminium ion that contains 0.5wt%) of 50g/L as anodic oxidation solution, be 12A/dm with current density ²DC voltage, under 50 ℃, 30 seconds condition, aluminium sheet is carried out anodized, form anodic oxidation coating.With reference to the table of comparisons that makes according to the relation of concentration of nitric acid and aluminium ion concentration, temperature, proportion and liquid conduction rate in advance, obtain strength of fluid according to temperature, proportion and conductance, by FEEDBACK CONTROL, add the nitric acid of water and 50wt%, make the concentration of anode oxidation treatment liquid keep stable.After this, wash with nozzle.

(8) reaming is handled

To be to soak 30 seconds in 13 50 ℃ the NaOH aqueous solution at pH value through the aluminium sheet after the anodized, and carry out reaming and handle.After this wash.

(9) hydrophilic surface is handled

With concentration is that No. 3 sodium silicate aqueous solutions of 2.5wt% were handled 10 seconds under 70 ℃ condition, carries out hydrophilic surface and handles.

After this, through washing, drying, obtain aluminium support body 1.

(Production Example 2 of supporter)

Handle except the aqueous solution that contains inorganic fluorine compounds and silicate compound, replace outside the hydrophilic surface of above-mentioned (9) handles, by obtaining aluminium support body 2 with the same method of supporter Production Example 1 with following (10).

(10) usefulness contains the processing of the aqueous solution of inorganic fluorine compounds and silicate compound

Employing pure water modulation, the aluminium sheet after the aqueous solution soaking reaming that makes the concentration of sodium fluoride and No. 3 sodium metasilicate reach 2wt% and 2.5wt% is respectively handled soaked 10 seconds under 100 ℃ condition.After this wash.

(supporter Production Example 3)

Except handle in the reaming of above-mentioned (8) and the hydrophilic surface processing of (9) between contain particle with the usefulness of following (11) the aqueous solution handle, by obtaining aluminium support body 3 with the same method of supporter Production Example 1.

(11) handle with the liquid that contains particle

Plate after handling with reaming is as negative electrode, and adopting the average grain diameter that contains 1wt% is that the suspension of the aluminium oxide particles of 30nm is an electrolyte, carries out the electrolytic treatments of 60 seconds burning voltages under the voltage of 110V, after this washes, drying, and carries out sealing of hole and handle.

(the supporter Production Example 1 that is used for comparative example)

Except the reaming of the anodized that replaces above-mentioned (7) with the anodized of following (7 ') and (8) is handled, use the aluminium support body 1 that obtains being used for comparative example with the same method of supporter Production Example 1.

(7 ') anodized

With sulfuric acid concentration be the aqueous solution (aluminium ion that contains 0.5wt%) of 170g/L as anodic oxidation solution, adopt DC voltage, be 5A/dm in current density ², aluminium sheet is carried out anodized under 43 ℃, 33 seconds the condition, form anodic oxidation coating.With reference to the table of comparisons that makes according to the relation of sulfuric acid concentration and aluminium ion concentration, temperature, proportion and liquid conduction rate in advance, obtain strength of fluid according to temperature, proportion and conductance, by FEEDBACK CONTROL, add the sulfuric acid of water and 50wt%, make the concentration of anode oxidation treatment liquid keep constant.After this, wash with nozzle.

(the supporter Production Example 2 that is used for comparative example)

Except handling, replace outside the aqueous solution that the usefulness of above-mentioned (10) contains inorganic fluorine compounds and silicate compound handles, by obtaining aluminium support body 2 with the same method of supporter Production Example 2 with the phosphate/inorganic fluorine compounds of following (12).

(12) handle with phosphate/inorganic fluorine compounds

Employing pure water modulation, the aluminium sheet after the aqueous solution soaking reaming that makes the concentration of sodium fluoride and sodium dihydrogen phosphate reach 0.1wt% and 10wt% is respectively handled soaked 10 seconds under 100 ℃ condition.After this wash.

The measurement method of porosity of＜anodic oxidation coating 〉

Obtain aluminium support body 1～3 and be used for the aluminium support body 1 of comparative example and the porosity of 2 anodic oxidation coating by following formula, be illustrated in the 2nd table.

Porosity (%)=(1-(oxide film thereon density/3.98)) * 100

Wherein, the density (g/cm of oxide film thereon ³) be the weight (g/cm of the oxide film thereon of per unit area ²) try to achieve divided by the thickness (cm) of oxide film thereon.The non-image part of the lithographic plate that the development treatment of above-mentioned supporter by original edition of lithographic printing plate described later obtained is cut into suitable size, be immersed in メ イ ソ Application (mason) liquid that constitutes by chromic acid/phosphoric acid, make the anodic oxidation coating dissolving, measure the forward and backward weight of dissolving, weight difference can be obtained the weight of the oxide film thereon of per unit area divided by the area of cutting.And the thickness of oxide film thereon is by the anodic oxidation coating of the non-image portion after scan microscope (T20, society of NEC system) the observation development treatment, surveys the mean value of the thickness at 50 places and obtains.

3.98 compile " density (the g/cm of the aluminium oxide of chemical handbook (ball is kind) according to Japanization association ³).

The measurement in the aperture of＜anodic oxidation coating surface micropore 〉

In each original edition of lithographic printing plate, the aperture of the anodic oxidation coating surface micropore of the non-image portion after the development treatment is to utilize scanning electron microscope (S-900, Hitachi society system) be 12kV at accelerating potential, not under the condition of evaporation, according to what obtain with the observed SEM photo of 150,000 times multiplying power.Select the aperture of the mean value of 50 micropores arbitrarily, be illustrated in the 2nd table as micropore.

1-2. the modulation of the synthetic and microcapsules of particulate polymer

(1) the particulate polymer is synthetic

Add 7.5g allyl methacrylate, 7.5g butyl methacrylate, (concentration is 9.84 * 10 to the 200ml polyoxyethylene nonyl phenol aqueous solution ^-3Mol/L), with 250rpm stir on one side, nitrogen replacement used on one side.After this liquid arrived 25 ℃, (concentration was 0.984 * 10 to add 10ml cerium (IV) ammonium salt aqueous solution ^-3Mol/L).At this moment, (concentration is 58.8 * 10 to add aqueous ammonium nitrate solution ^-3Mol/L), pH value is adjusted to 1.3～1.4.After this, stirred 8 hours, thereby obtain containing the liquid of particulate polymer.The concentration of the solid constituent of the liquid that obtains is 9.5wt%, and the average grain diameter of particulate polymer is 0.2 μ m.

(2) modulation of microcapsules

Copolymer (mol ratio is 7/3) and 0.1g surfactant (pioneer A41C with 40g XDI, 10g trimethylolpropane diacrylate, 10g allyl methacrylate and butyl methacrylate, this grease of bamboo society system) is dissolved in the 60g ethyl acetate, forms oil-phase component.On the other hand, polyvinyl alcohol (PVA205, the Network ラ レ society system) aqueous solution of modulation 120g4wt% is as water-phase component.Above-mentioned oil-phase component and water-phase component are dropped in the homogenizer, carry out emulsification with 10000rpm.After this, add 40g water, at room temperature stirred 30 minutes, stirred 3 hours down at 40 ℃ again, thereby obtain microcapsules liquid.The concentration of the solid constituent of the microcapsules liquid that obtains is 20wt%, and the average grain diameter of microcapsules is 0.2 μ m.

1-3. the making of original edition of lithographic printing plate

(embodiment 1～3 and comparative example 1,2)

By at the above-mentioned aluminium support body that obtains 1～3 and be used for the coating liquid of the following heat sensing layer of forming of coating (1) on the aluminium support body 1 and 2 of comparative example, with baking oven 60 ℃ dry 150 seconds down, thereby obtain the original edition of lithographic printing plate of embodiment 1～3 and comparative example 1 and 2.The drying coated amount of heat sensing layer (1) is 0.5g/m ²

The composition of＜heat sensing layer (1) coating liquid 〉

. contain the liquid 5g (solid constituent) of above-mentioned synthetic particulate polymer

. poly-hydroxyethyl acrylate (weight average molecular weight 2.5 ten thousand) 0.5g

. photo-thermal conversion agent (IR-11 of this specification record) 0.3g

. water 100g

(embodiment 4～6 and comparative example 3 and 4)

By at the above-mentioned aluminium support body that obtains 1～3 and be used for the coating liquid of the following heat sensing layer of forming of coating (2) on the aluminium support body 1 and 2 of comparison, with baking oven 60 ℃ dry 150 seconds down, thereby obtain the original edition of lithographic printing plate of embodiment 4～6 and comparative example 3 and 4.The drying coated amount of heat sensing layer (2) is 0.7g/m ²

The composition of the coating liquid of＜heat sensing layer (2) 〉

. above-mentioned synthetic microcapsules liquid 5g (solid constituent)

. trimethylolpropane triacrylate 3g

. photo-thermal conversion agent (IR-11 of this specification record) 0.3g

. water 60g

.1-methoxyl group-2-propyl alcohol 40g

1-4. the mensuration of the atomicity of carbon and aluminium in the cutting plane of the anodic oxidation coating behind the heat sensing layer than (C/Al) is set

As described below, for the original edition of lithographic printing plate of embodiment 1～6 and comparative example 1～4, the ratio (C/Al) of the carbon in the mensuration cutting plane and the atomicity of aluminium.

Before being about to analysis, original edition of lithographic printing plate is bent nearly 180 degree, thereby form the cutting plane of anodic oxidation coating, be fixed in the attached specimen holder of auger electrons spectroscopy apparatus, and in the gatherer, carry out the auger electrons spectrum analysis.

Obtain I according to the chart that obtains _cAnd I _AlS _cValue be 0.076, S _AlValue be 0.105, with the I that obtains _cAnd I _AlValue substitution following formula (1), thereby calculate C/Al.The result is illustrated in the 2nd table.

Also have, C/Al is that adjust the distance 5 points of about 0.2 μ m position, interface of the heat sensing layer of cutting plane of anodic oxidation coating and anodic oxidation coating carry out the auger electrons spectrum analysis, obtains its mean value.

The condition of auger electrons spectrum analysis is as follows.

Measure machine: FE AES type SMART-200, A Lu send out in eight storehouses society's system with (ア Le バ Star Network Off ア イ)

Irradiation electric current: about 10nA

Accelerating potential: 10kV

Irradiating electron beam diameter: focus on

Chamber inner pressure: about 1 * 10 ^-10Torr (about 1.33 * 10 ^-8Pa)

Detection range: 20～2020eV, 0eV/step, 20ms/step

The voltage of amplifier: 2250V

1-5. the mensuration of speed

(embodiment 1～3 and comparative example 1 and 2)

Employing is mounted with the turning adjuster 3244VFS of Network レ オ society system of the infrared semiconductor laser of water-cooled 40W, but is the original edition of lithographic printing plate that develops on the machine of output and exposure embodiment 1～3 and comparative example 1 and 2 under the condition of 2400dpi in resolution ratio.At this moment, can change the energy of the space of a whole page, estimate speed according to the lowest exposure amount that can form image by the rotation number that changes outer surface roller.The result is illustrated in the 2nd table.

(embodiment 4～6 and comparative example 3 and 4)

Employing is mounted with the Luxel T-9000CTP of photo Co., Ltd. of Fuji system of multi-channel laser head, but is the original edition of lithographic printing plate that develops on the machine of output and exposure embodiment 4～6 and comparative example 3 and 4 under the condition of 2400dpi in resolution ratio.At this moment, the output by changing every Shu Guang and the rotation number of outer surface roller are estimated speed according to the lowest exposure amount that can form image.The result is illustrated in the 2nd table.

1-6. printing test

After the original edition of lithographic printing plate of embodiment 1～6 and comparative example 1～4 exposed as mentioned above, do not carry out any processing, promptly be installed on the cylinder of breathing out the printing machine SOR-M that has carried on the back storehouse (Ha イ デ Le ベ Le グ society) system in the special road of clothing, after supplying with dumping processing solution, supply with printing ink, resupply paper, print test.In the original edition of lithographic printing plate of all embodiment, undoubtedly can develop on the realization machine, also can print.

In above-mentioned printing test, scumming, set-off (adhering to printing ink) and anti-seal are estimated by following method.Its result is illustrated respectively in the 2nd table.

(1) scumming

In the printing test, adjust the level scale of printing machine, estimate scumming according to the scale of the water level that produces scumming.The level scale that produces scumming is done to make zero △ less than 3 o'clock notes zero, 2 or more less than 2 o'clock notes, makes △ less than 4 o'clock notes 3 or more, 4 remember when above work *.

(2) set-off (adhering to printing ink)

Only supply with printing ink to galley after developing on the machine, after this resupply dumping processing solution, and wipe printing ink, obtain the printing number of pages till obtaining distinct printed matter, the few more anti-set-off of number of pages (adhering to printing ink) is good more.

(3) anti-seal

The printing number of pages of the printed matter by the distinctness that obtains is estimated anti-seal.How anti-the more seal of printing number of pages be good more.

From the 2nd table as can be seen, the speed of original edition of lithographic printing plate of the present invention (embodiment 1～6) is good, is difficult to take place scumming, and anti-set-off (adhering to printing ink) and anti-seal are all fine.Relative therewith, (comparative example 1～4) is set when C/Al is excessive in the cutting plane of the anodic oxidation coating behind the heat sensing layer or scumming takes place easily, anti-set-off (adhering to printing ink) is poor, or the low anti-seal of speed is poor.

[table 2]

The 2nd table

	Supporter	Heat sensing layer	C/Al	Porosity (%)	Micropore size (nm)	Scumming	Set-off (page or leaf)	Speed (m/cm 2)	Anti-seal (ten thousand pages)
										Embodiment 1	1	(1)	0.88	60	40	○△	19	190	2.2
Embodiment 2	2	(1)	0.65	55	8	○	15	180	1.9
										Embodiment 3	3	(1)	0.62	40	12	○	16	180	2.0
Comparative example 1	4	(1)	1.09	15	10	○	19	370	0.1
										Comparative example 2	5	(1)	1.10	40	15	×	48	250	0.5
Embodiment 4	1	(2)	0.88	60	40	○△	19	230	1.8
										Embodiment 5	2	(2)	0.65	55	8	○	15	220	1.7
Embodiment 6	3	(2)	0.62	40	12	○	16	200	2.0
										Comparative example 3	4	(2)	1.09	15	10	○△	19	390	0.1
Comparative example 4	5	(2)	1.10	40	15	×	48	270	0.5

2-1. the modulation of original edition of lithographic printing plate

(embodiment 7)

Adopt the aluminium sheet of stipulating among the JIS A1050 of thickness of slab 0.24mm as substrate, carry out following processing successively, make aluminium support body.

(a) carry out corrosion treatment with basic solvent

With the naoh concentration is that 26wt%, aluminium ion concentration are that 6.5wt%, temperature are 70 ℃ solution, with nozzle aluminium sheet is carried out corrosion treatment, aluminium sheet dissolving 6g/m ²After this wash with nozzle.

(b) go spot to handle

With temperature is that 30 ℃ concentration of nitric acid is that the aqueous solution (containing the 0.5wt% aluminium ion) of 1wt% goes spot to handle by nozzle, after this washes with nozzle.The aforementioned used aqueous solution of nitric acid of spot that goes can utilize in aqueous solution of nitric acid waste liquid in the electrochemical surface alligatoring operation that adopts alternating current.

(c) electrochemical surface coarsening is handled

Alternating current with 60Hz carries out electrochemical surface coarsening processing continuously.The electrolyte of this moment is that concentration of nitric acid is that 1wt%, temperature are 50 ℃ the aqueous solution (contain aluminium ion 0.5wt%, ammonium concentration is 0.007wt%).The waveform of AC power as shown in Figure 2, current value is 2msec from the 0 time T P that reaches peak value, the DUTY ratio is 1: 1, adopts trapezoidal square wave ac, handles as the utmost point being carried out electrochemical surface coarsening with carbon electrode.Impressed current anode adopts ferrite.The electrolytic cell that uses adopts 2 as shown in Figure 3.

Current density is 30A/dm at the current peak place ², the summation of the electric weight when aluminium sheet is anode is 270C/dm ²5% of the electric current that flows out from power supply is diverted to impressed current anode.

After this wash with nozzle.

(d) corrosion treatment

The NaOH that with concentration is 26wt% is that 6.5wt%, temperature are that 70 ℃ solution carries out corrosion treatment by nozzle to aluminium sheet, aluminium sheet dissolving 0.2g/m at aluminium ion concentration ²Thereby the spot composition based on aluminium hydroxide that generates when adopting alternating current to carry out the electrochemical surface alligatoring before removing, and the marginal portion of the pit of dissolving generation make the marginal portion become smooth.After this wash with nozzle.

(e) go spot to handle

With temperature is that 60 ℃ sulfuric acid concentration is that the aqueous solution (containing aluminium ion 0.5wt%) of 25wt% goes spot to handle by nozzle, after this, washes and dry by nozzle, thereby obtains substrate 1.

(f) anodized

At sulfuric acid concentration is in the electrolyte of 170g/L, is that 33 ℃, current density are 5A/dm in temperature ²Condition under, with direct current substrate 1 is carried out 66 seconds anodized, form anodic oxidation coating.

(g) reaming is handled

It is in 13 the sodium hydrate aqueous solution 60 seconds that substrate after the anodized 1 is immersed in 30 ℃ pH value, after this washes and dry, carries out reaming subsequently and handles.

(h) formation of particle layer

Contain the Al that average grain diameter is 10～20nm with the pure water dilution ₂O ₃The alumina sol dispersion liquid of particle (alumina sol-520, daily output chemical industry society system, solid constituent (Al ₂O ₃) concentration be 20wt%), make the concentration of solid constituent reach 0.2wt%, be to handle substrate 14 seconds after reaming is handled with soaked with liquid under 70 ℃ the condition in temperature, after this wash and dry, form particle layer.

(i) hydrophilicity-imparting treatment

Substrate 1 continuous dipping in the aqueous solution of the 2.5wt% of No. 3 sodium metasilicate behind the formation particle layer carries out hydrophily and handles (silicidation).The temperature of treatment fluid is 70 ℃, and the time of immersion treatment is 10 seconds.After this, wash and drying, on anodic oxidation coating, form particle layer, thereby obtain the supporter of lithographic plate with nozzle.

(j) formation of heat sensing layer

As follows, coating heat sensing layer coating liquid and dry on the supporter of above-mentioned lithographic plate, thus obtain original edition of lithographic printing plate.

Modulate the heat sensing layer coating liquid of following composition, on the supporter of above-mentioned lithographic plate master, apply this heat sensing layer coating liquid 1, make that dried coating amount (coating amount of heat sensing layer) is 0.7g/m with coater ², the usefulness baking oven descended dry 60 seconds at 100 ℃, formed heat sensing layer, thereby obtained original edition of lithographic printing plate.

The composition of＜heat sensing layer coating liquid 〉

. aftermentioned microcapsules liquid 25g (solid constituent 5g)

. trimethylolpropane triacrylate 3g

. infrared ray absorbing dyestuff (IR-11) 0.3g of this specification record

. water 60g

.1-methoxyl group-2-propyl alcohol 1g

＜microcapsules 〉

Copolymer (mol ratio is 7/3) and 0.1g surfactant (pioneer A41C with 40g XDI, 10g trimethylolpropane diacrylate, 10g allyl methacrylate and butyl methacrylate, this grease of bamboo society system) is dissolved in the 60g ethyl acetate, forms oil-phase component.Modulate the aqueous solution of 120g4wt% polyvinyl alcohol (PVA205, Network ラ レ society system) on the other hand, as water-phase component.Above-mentioned oil-phase component and water-phase component are dropped in the homogenizer, with 10000rpm emulsification 10 minutes.After this, add 40g water, at room temperature stirred 30 minutes, and then stirred 3 hours down, thereby obtain microcapsules liquid at 40 ℃.The concentration of the solid constituent of the microcapsules liquid that obtains is 20wt%, and the average grain diameter of microcapsules is 0.5 μ m.

(embodiment 8～10)

In the forming process of above-mentioned (h) particle layer, except colloidal silica dispersion liquid ((being special storehouse thing) ス ノ-テ Star Network ス N, (being special storehouse thing) ス ノ-テ Star Network ス XL and (being special storehouse thing) ス ノ-テ Star Network ス ZL with average grain diameter shown in the 3rd table, all be daily output chemical society system) replace beyond the dispersion liquid of alumina sol, obtain original edition of lithographic printing plate by the method identical with embodiment 7.

(embodiment 11,12)

In the forming process of above-mentioned (h) particle layer, except Al with average grain diameter shown in the 3rd table ₂O ₃The aqueous suspension of particle replaces beyond the dispersion liquid of alumina sol, obtains original edition of lithographic printing plate by the method identical with embodiment 7.

(embodiment 13)

Be immersed in the phosphoric acid polyethylene aqueous solution of 1wt% 10 seconds except the substrate 1 after 50 ℃ down will form particle layer, replace beyond the hydrophilicity-imparting treatment of above-mentioned (i) thereby carry out hydrophilicity-imparting treatment, obtain original edition of lithographic printing plate by the method identical with embodiment 7.

(embodiment 14)

In the forming process of above-mentioned (h) particle layer, except with average grain diameter being colloidal silica dispersion liquid ((being Nuo Te storehouse thing) ス ノ-テ Star Network ス N of 10～20 μ m, produce chemical society system daily) replace beyond the dispersion liquid of alumina sol, obtain original edition of lithographic printing plate by the method identical with embodiment 13.

(embodiment 15)

Except the hydrophilicity-imparting treatment operation of not carrying out above-mentioned (i), obtain original edition of lithographic printing plate by the method identical with embodiment 7.

(embodiment 16)

Except the hydrophilicity-imparting treatment operation of not carrying out above-mentioned (i), obtain original edition of lithographic printing plate by the method identical with embodiment 8.

(embodiment 17～19)

In the forming process of above-mentioned (h) particle layer, except the concentration with the solid constituent after the alumina sol dispersion liquid dilution became the concentration of the solid constituent shown in the 3rd table respectively, the method by similarly to Example 7 obtained original edition of lithographic printing plate.

(embodiment 20 and 21)

In the forming process of above-mentioned (h) particle layer, except temperature being become the temperature shown in the 3rd table respectively, the method by similarly to Example 7 obtains original edition of lithographic printing plate.

(embodiment 22 and 23)

In the forming process of above-mentioned (h) particle layer, except soak time being become the soak time shown in the 3rd table respectively, the method by similarly to Example 7 obtains original edition of lithographic printing plate.

(embodiment 24)

Except the reaming treatment process of not carrying out above-mentioned (g), obtain original edition of lithographic printing plate by the method identical with embodiment 7.

(embodiment 25～27)

In the reaming processing procedure of above-mentioned (g), except soak time being become the soak time shown in the 3rd table respectively, the method by similarly to Example 7 obtains original edition of lithographic printing plate.

(embodiment 28)

In the forming process of above-mentioned (h) particle layer, except the mixed liquor dilution with pure water 10wt% and methyl alcohol 90wt% contains the Al that average grain diameter is 10～20nm ₂O ₃(alumina sol-520 is produced chemical society system daily, solid constituent (Al to the alumina sol dispersion liquid of particle ₂O ₃) concentration be 20wt%), make that the concentration of solid constituent is substrate 1 spin coated 10 seconds after liquid that 0.2wt% obtains is handled reaming with 180rpm by coating machine (Bei Cun description plate-making articles for use are made society's system), after this use baking oven (thermostat SHP-201, step on eight to like being to accompany chi storehouse ( バ イ エ ス ペ Star Network society system) following dry 1 minute at 120 ℃, replace beyond the immersion treatment thereby form particle layer, the method by similarly to Example 7 obtains original edition of lithographic printing plate.

(embodiment 29～31)

Form in the process of particle layer at above-mentioned (h), colloidal silica dispersion liquid ((being Nuo Te storehouse thing) ス ノ-テ Star Network ス N with average grain diameter shown in the 5th table, (being Nuo Te storehouse thing) ス ノ-テ Star Network ス XL and (being Nuo Te storehouse thing) ス ノ-テ Star Network ス ZL, all be daily output chemical society system) replace beyond the dispersion liquid of alumina sol, obtain original edition of lithographic printing plate by the method identical with embodiment 28.

(embodiment 32 and 33)

In the forming process of above-mentioned (h) particle layer, except Al with average grain diameter shown in the 5th table ₂O ₃The aqueous suspension of particle replaces beyond the dispersion liquid of alumina sol, obtains original edition of lithographic printing plate by the method identical with embodiment 28.

(embodiment 34)

Be immersed in the phosphoric acid polyethylene aqueous solution of 1wt% 10 seconds except the substrate 1 after 50 ℃ down will form particle layer, replace beyond the hydrophilicity-imparting treatment of above-mentioned (i) thereby carry out hydrophilicity-imparting treatment, obtain original edition of lithographic printing plate by the method identical with embodiment 28.

(embodiment 35)

In the forming process of above-mentioned (h) particle layer, except with average grain diameter being colloidal silica dispersion liquid (the ス ノ-テ Star Network ス N of 10～20 μ m, produce chemical society system daily) replace beyond the dispersion liquid of alumina sol, obtain original edition of lithographic printing plate by the method identical with embodiment 34.

(embodiment 36)

Except the hydrophilicity-imparting treatment operation of not carrying out above-mentioned (i), obtain original edition of lithographic printing plate by the method identical with embodiment 28.

(embodiment 37)

Except the hydrophilicity-imparting treatment operation of not carrying out above-mentioned (i), obtain original edition of lithographic printing plate by the method identical with embodiment 29.

(embodiment 38～40)

Form in the process of particle layer at above-mentioned (h), except the concentration with the solid constituent after the dilution of alumina sol dispersion liquid became the concentration of the solid constituent shown in the 5th table respectively, the method by similarly to Example 28 obtained original edition of lithographic printing plate.

(embodiment 41)

Except the reaming treatment process of not carrying out above-mentioned (g), obtain original edition of lithographic printing plate by the method identical with embodiment 28.

(embodiment 42～44)

In the reaming processing procedure of above-mentioned (g), except soak time being become the soak time shown in the 5th table respectively, the method by similarly to Example 28 obtains original edition of lithographic printing plate.

(embodiment 45)

Form in the process of particle layer at above-mentioned (h), except the substrate 1 after handling with reaming as negative electrode, be the Al of 15nm with the average grain diameter that contains 0.5wt% ₂O ₃The aqueous suspension of particle is as electrolyte, carries out 60 seconds electrolytic treatments with the burning voltage of 110V voltage, after this washes and dry, thereby forms beyond the particle layer, and the method by similarly to Example 7 obtains original edition of lithographic printing plate.

2-2. observe the cutting plane of original edition of lithographic printing plate

In each original edition of lithographic printing plate, be 12kV with scanning electron microscope (S-900, Hitachi's system) at accelerating potential, do not observe the cutting plane of the non-image part after the development treatment under the condition of evaporation with 5～150,000 times multiplying power.

The SEM photo of the cutting plane of the non-image part after the development treatment of the original edition of lithographic printing plate that obtains by embodiment 7 as shown in Figure 5.Have particle layer 5 on the aluminium support body 4 that forms in that anodic oxidation coating 3 is set on the aluminium sheet 2 as can be seen.And the micropore 7 on the anodic oxidation coating 3 has been stopped up by particle layer 5 as can be seen, but inside still has hole.Be not only the cutting plane of original edition of lithographic printing plate in addition among Fig. 5, can also see the surface 8 of non-image part.

Original edition of lithographic printing plate for embodiment 8～45 also is same.

2-3. the micropore size on the anodic oxidation coating surface of original edition of lithographic printing plate

In each original edition of lithographic printing plate, the micropore size on the anodic oxidation coating surface by the non-image part after the development treatment of obtaining with above-mentioned same method is illustrated in the 3rd and the 5th table.

2-4. the porosity of the anodic oxidation coating of original edition of lithographic printing plate

In each original edition of lithographic printing plate, the porosity by the anodic oxidation coating obtained with above-mentioned same method is illustrated in the 3rd and the 5th table.

2-5. the pyroconductivity of the hydrophilic particles of the particle layer of original edition of lithographic printing plate

The pyroconductivity of the hydrophilic particles shown in the 3rd and the 5th table edit " the chemical handbook that " cermet technical manual newly " that " new cermet dictionary ", following process technology the 136th committee of JSPS edit and Japanization association edit according to new cermet dictionary editorial board.

2-6. the mensuration of the atomicity of carbon and aluminium in the cutting plane of the anodic oxidation coating behind the heat sensing layer than (C/Al) is set

In the original edition of lithographic printing plate of embodiment 7～45, by the atomicity of carbon in the cutting plane and aluminium being measured than (C/Al) with above-mentioned same method.The result is illustrated in the 3rd and the 5th table.

2-7. the speed of original edition of lithographic printing plate

With CREO society make pounce on Le Te society step on-when join society step on-(プ レ-ト セ Star -Trendsetter3244F) (carry the multi-beam of 192 paths) after the various parameters of adjustment (Sr, Sd, bmslope, bmcurve) exposes to the image of each original edition of lithographic printing plate with 2400dpi.Exposure is to be undertaken by revolution that changes cylinder and power output interimly.After the exposure, on printing machine, carry out development treatment, with the energy that can form 1% site speed as original edition of lithographic printing plate.The result is illustrated in the 4th and the 6th table.

2-8. anti-seal and anti-set-off

Each original edition of lithographic printing plate after the exposure is installed on the printing machine, supplies with printing ink behind the supply dumping processing solution, carries out development treatment on printing machine, and prints continuously.Pounce on Lin Te (ス プ リ Application ト) here when printing machine adopts the printing machine that little gloomy printing machine society makes, the Geos printing ink that printing ink adopts big Japanese ink chemical industry society to make, water diluent (1: the 100) 90vol% of the dumping processing solution EU-3 that dumping processing solution employing Fuji's description film (strain) is made and the mixture of isopropyl alcohol 10vol%, printing paper adopts the measured paper of matter.

Print under these conditions, measure image portion and do not adhere to of the evaluation of the number of pages of printing ink as anti-seal.The result is illustrated in the 4th and the 6th table.

After printing 500 pages under these conditions, take off lithographic plate from printing machine, in indoor placement after 30 minutes, be installed to once more and begin to supply with dumping processing solution and printing ink, paper on the printing machine simultaneously, mensuration is not adhered to printing ink in the corresponding zone of non-image part that is formed on printing, the number of pages that does not have the waste paper till the non-image part of scumming is as the evaluation of anti-scumming.The few more anti-scumming of the number of pages of waste paper is good more.The result is illustrated in the 4th and the 6th table.

Show as the 3rd～the 6th and to show that speed, anti-seal and the anti-scumming of the original edition of lithographic printing plate that is obtained by the manufacture method (embodiment 7～45) of the original edition of lithographic printing plate of the 2nd scheme of the present invention are all fine.

(embodiment 45) speed and Nai Yin are fine when by electrolytic treatments particle layer being set, but compare with the situation (embodiment 11 and 32) that particle layer is set by immersion or coating, and its anti-scumming is relatively poor.

[table 3]

The 3rd table

	Anodic oxidation coating					Particle layer
														Electrolyte	Reaming is handled		Micropore size (nm)	Porosity (%)	The kind of treatment fluid	The average grain diameter of particle (nm)	The pyroconductivity of particle (W/ (m*k)	The formation method	Treatment fluid solid component concentration (quality %)	Treatment fluid temperature (C)	Processing time	C/Al
	Temperature (℃)	Time (second)
			Embodiment 7	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.2		70	14											0.64
Embodiment 8	Sulfuric acid	30												60			15	50	Be Nuo Te storehouse thing N	10-20	10	Immersion treatment	0.2	70	14	0.68
			Embodiment 9	Sulfuric acid	30	60	15	50	Be Nuo Te storehouse thing XL	40-60	10	Immersion treatment	0.2		70	14											0.78
Embodiment 10	Sulfuric acid	30												60			15	50	Be Nuo Te storehouse thing ZL	70-100	10	Immersion treatment	0.2	70	14	0.82
			Embodiment 11	Sulfuric acid	30	60	15	50	Al 2O 3Aqueous suspension	15	36	Immersion treatment	0.2		70	14											0.74
Embodiment 12	Sulfuric acid	30												60			15	50	Al 2O 3Aqueous suspension	750	36	Immersion treatment	0.2	70	14	0.88

Embodiment 13	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	14	0.58
														Embodiment 14	Sulfuric acid	30	60	15	50	Be Nuo Te storehouse thing N	10-20	10	Immersion treatment	0.2	70	14	0.54
Embodiment 15	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	14	0.64
														Embodiment 16	Sulfuric acid	30	60	15	50	Be Nuo Te storehouse thing N	10-20	10	Immersion treatment	0.2	70	14	0.54
Embodiment 17	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.01	70	14	0.92
														Embodiment 18	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	5	70	14	0.64
Embodiment 19	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	10	70	14	0.72
														Embodiment 20	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.2	10	14	0.59
Embodiment 21	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.2	85	14	0.69
														Embodiment 22	Sulfuric acid	30	60	15	50	Alumina sol	10-20	36	Soak	0.2	70	2	0.64

						520			Handle
														Embodiment 23	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	120	0.58
Embodiment 24	Sulfuric acid	-	-	7	16	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	14	0.59
														Embodiment 25	Sulfuric acid	30	30	10	25	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	14	0.69
Embodiment 26	Sulfuric acid	30	65	18	60	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	14	0.68
														Embodiment 27	Sulfuric acid	30	70	20	75	Alumina sol 520	10-20	36	Immersion treatment	0.2	70	14	0.79

[table 4]

The 4th table

	Hydrophilicity-imparting treatment	Speed (mJ/cm 2)	Anti-seal (thousand pages)	Scumming (page or leaf)
					Embodiment 7	Silicate	250	15	18
Embodiment 8	Silicate	250	14	18
					Embodiment 9	Silicate	250	14	18
Embodiment 10	Silicate	250	13	18
					Embodiment 11	Silicate	250	13	20
Embodiment 12	Silicate	250	12	20
					Embodiment 13	The polyvinyl phosphonic acids	250	14	20
Embodiment 14	The polyvinyl phosphonic acids	250	14	20
					Embodiment 15	Do not have	250	15	23
Embodiment 16	Do not have	250	14	23
					Embodiment 17	Silicate	300	12	20
Embodiment 18	Silicate	250	14	15
					Embodiment 19	Silicate	250	12	23
Embodiment 20	Silicate	300	12	18
					Embodiment 21	Silicate	250	14	23
Embodiment 22	Silicate	300	12	20
					Embodiment 23	Silicate	280	15	23
Embodiment 24	Silicate	320	12	15
					Embodiment 25	Silicate	280	12	15
Embodiment 26	Silicate	250	15	18
					Embodiment 27	Silicate	280	15	20

[table 5]

The 5th table

	Anode acidifying tunicle					Particle layer
												Electrolyte	Reaming is handled		Micropore size (nm)	Porosity (%)	The kind of treatment fluid	The average diameter of particle (nm)	The pyroconductivity of particle (W/ (m K)	The formation method	Treatment fluid solid component concentration (quality %)	C/Al
	Temperature (C)	Time (second)
			Embodiment 28	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36		Coating	0.2									0.62
Embodiment 29	Sulfuric acid	30										60			15	50	Be Nuo Te storehouse thing N	10-20	10	Coating	0.2	0.64
			Embodiment 30	Sulfuric acid	30	60	15	50	Be Nuo Te storehouse thing XL	40-60	10		Coating	0.2									0.72
Embodiment 31	Sulfuric acid	30										60			15	50	Be Nuo Te storehouse thing ZL	70- 100	10	Coating	0.2	0.83
			Embodiment	Sulfuric acid	30	60	15	50	Al 2O 3Water	15	36		Coating	0.2									0.72

32						Suspension
												Embodiment 33	Sulfuric acid	30	60	15	50	Al 2O 3Aqueous suspension	750	36	Coating	0.2	0.88
Embodiment 34	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Coating	0.2	0.58
												Embodiment 35	Sulfuric acid	30	60	15	50	Be Nuo Te storehouse thing N	10-20	10	Coating	0.2	0.52
Embodiment 36	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Coating	0.2	0.57
												Embodiment 37	Sulfuric acid	30	60	15	50	Be Nuo Te storehouse thing N	10-20	10	Coating	0.2	0.53
Embodiment 38	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Coating	0.01	0.89
												Embodiment 39	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Coating	5	0.62

Embodiment 40	Sulfuric acid	30	60	15	50	Alumina sol 520	10-20	36	Coating	10	0.74
												Embodiment 41	Sulfuric acid			7	16	Alumina sol 520	10-20	36	Coating	0.2	0.58
Embodiment 42	Sulfuric acid	30	30	10	25	Alumina sol 520	10-20	36	Coating	0.2	0.68
												Embodiment 43	Sulfuric acid	30	65	18	60	Alumina sol 520	10-20	36	Coating	0.2	0.62
Embodiment 44	Sulfuric acid	30	70	20	75	Alumina sol 520	10-20	36	Coating	0.2	0.69
												Embodiment 45	Sulfuric acid	30	60	15	50	Al 2O 3Aqueous suspension	15	36	Electrolysis	0.5	0.72

[table 6]

The 6th table

	Hydrophilicity-imparting treatment	Speed (mJ/cm 2)	Anti-seal (thousand pages)	Anti-scumming (page or leaf)
					Embodiment 28	Silicate	250	16	20
Embodiment 29	Silicate	250	15	18
					Embodiment 30	Silicate	250	15	18
Embodiment 31	Silicate	250	15	18
					Embodiment 32	Silicate	250	13	20
Embodiment 33	Silicate	250	12	20
					Embodiment 34	The polyvinyl phosphonic acids	250	15	20
Embodiment 35	The polyvinyl phosphonic acids	250	15	20
					Embodiment 36	Do not have	250	16	25
Embodiment 37	Do not have	250	15	25
					Embodiment 38	Silicate	300	12	20
Embodiment 39	Silicate	250	14	20
					Embodiment 40	Silicate	250	14	23
Embodiment 41	Silicate	320	12	18
					Embodiment 42	Silicate	280	14	18
Embodiment 43	Silicate	250	16	20
					Embodiment 44	Silicate	280	15	25
Embodiment 45	Silicate	300	12	45

[effect of invention]

The original edition of lithographic printing plate of the present invention's the first scheme since the value that C/Al in the cutting plane of the anodic oxidation coating behind the recording layer is set below setting, therefore has development property on the good machine, speed is high, and table shows Gao Naiyin, be not prone to the scumming phenomenon during printing, and anti-set-off (adhering to printing ink) is good. At this moment, employing is carried out image exposure by laser, and be installed on the printing machine and print, or carry out image exposure with laser again after being installed on the printing machine, and the Plate making printing method of the lithographic plate of the present invention of printing need not separately development treatment again, can develop at printing machine, and can continue printing, therefore very useful.

In addition, because the value of the C/Al in the cutting plane of the anodic oxidation coating of original edition of lithographic printing plate after recording layer is set of the first scheme of the present invention is below setting, therefore when even the light exposure of infrared laser is low and the liquid inductance of developer solution when low, dissolubility with respect to developer solution also can improve, its result can improve speed, increase the tolerance of developing, even residual film is also less when hanging down exposure, non-image part also is difficult for scumming.

In addition, original edition of lithographic printing plate of the present invention since the value that the C/Al in the cutting plane of the anodic oxidation coating after the recording layer is set below setting, therefore the not dissolution rate for the developer solution in the laser explosure part increases, and its result causes speed to increase, and anti-seal is better.

Adopt the manufacture method of the original edition of lithographic printing plate of alternative plan of the present invention in image forms, to utilize expeditiously heat, can obtain ISO, the good and particularly preferred original edition of lithographic printing plate of anti-scumming of anti-seal. Thereby this original edition of lithographic printing plate both also went for hot negative-type applicable to hot positive type, also was applicable in addition developable on the machine, and was therefore very useful.

Claims (17)

1, a kind of original edition for lithographic printing, it is characterized in that: forming on the aluminium sheet on the support device for lithographic printing plate of anodic oxidation coating, setting is by the infrared laser original edition of lithographic printing plate that writeable recording layer forms that exposes, wherein in the cutting plane of this anodic oxidation coating after this recording layer is set, by the atomicity of the carbon of following formula (1) expression and aluminium than below 1.0:

C/Al＝(1 _c/S _c)/(I _al/S _al) (1)

I _c: the auger electrons derivative-type peak of carbon (KLL) is to peak intensity

I _Al: the auger electrons derivative-type peak of aluminium (KLL) is to peak intensity

S _c: the relative sensitivity coefficient of the auger electrons of carbon (KLL)

S _Al: the relative sensitivity coefficient of the auger electrons of aluminium (KLL).

2, a kind of original edition of lithographic printing plate according to claim 1 is characterized in that: the porosity of the anodic oxidation coating before aforementioned recording layer is set is 20～70%, and the diameter of micropore on surface that exposes this anodic oxidation coating is below 15nm.

3, a kind of original edition of lithographic printing plate according to claim 1 and 2 is characterized in that: have successively on the aluminium support body that forms on the aluminium sheet anodic oxidation coating being set by average grain diameter be the particle layer that constitutes of the hydrophilic particles of 8～800nm, and by the infrared laser writeable recording layer that exposes.

4, a kind of original edition of lithographic printing plate according to claim 1 and 2, it is characterized in that: aforementioned recording layer is to contain

(a) have the particulate polymer of heat reactivity functional group, or

(b) inside comprises the heat sensing layer of the microcapsules of the compound with heat reactivity functional group.

5, a kind of original edition of lithographic printing plate according to claim 3, it is characterized in that: aforementioned recording layer is to contain

(a) have the particulate polymer of heat reactivity functional group, or

(b) inside comprises the heat sensing layer of the microcapsules of the compound with heat reactivity functional group.

6, a kind of method of making the described original edition of lithographic printing plate of claim 3, it is characterized in that: wherein the aluminium support body that on the aluminium sheet anodic oxidation coating is set and forms is immersed in and contains in the liquid of hydrophilic particles that average grain diameter is 8-800nm, and on this aluminium support body, particle layer is set, will be arranged on this particle layer by the infrared laser writeable recording layer that exposes again.

7, a kind of method of making the described original edition of lithographic printing plate of claim 3, it is characterized in that: wherein coating contains the liquid that average grain diameter is the hydrophilic particles of 8～800nm on the aluminium support body that forms on the aluminium sheet anodic oxidation coating being set, and on this aluminium support body, particle layer is set, will be arranged on this particle layer by the infrared laser writeable recording layer that exposes again.

8, a kind of manufacture method according to claim 6 or 7 described original edition of lithographic printing plate is characterized in that: wherein after particle layer is set, carry out hydrophilicity-imparting treatment before recording layer is set.

9, a kind of manufacture method according to claim 6 or 7 described original edition of lithographic printing plate, it is characterized in that: wherein the pyroconductivity of aforementioned hydrophilic particles is below 60W/ (mK).

10, a kind of manufacture method of original edition of lithographic printing plate according to claim 8 is characterized in that: wherein the pyroconductivity of aforementioned hydrophilic particles is below 60W/ (mK).

11, a kind of original edition of lithographic printing plate that obtains by the manufacture method of claim 6 or 7 or 10 described original edition of lithographic printing plate.

12, a kind of original edition of lithographic printing plate that obtains by the manufacture method of the described original edition of lithographic printing plate of claim 8.

13, a kind of original edition of lithographic printing plate that obtains by the manufacture method of the described original edition of lithographic printing plate of claim 9.

14, a kind of plate-making of lithographic plate and printing process, after wherein the original edition of lithographic printing plate described in claim 1 or 2 or 5 or 12 or 13 being carried out image exposure by laser, be directly installed on the printing machine and print, carry out image exposure with laser after perhaps on being installed to printing machine, more directly printing.

15, a kind of plate-making of lithographic plate and printing process, after wherein the original edition of lithographic printing plate described in the claim 3 being carried out image exposure by laser, be directly installed on the printing machine and print, carry out image exposure with laser after perhaps on being installed to printing machine, more directly printing.

16, a kind of plate-making of lithographic plate and printing process, after wherein the original edition of lithographic printing plate described in the claim 4 being carried out image exposure by laser, be directly installed on the printing machine and print, carry out image exposure with laser after perhaps on being installed to printing machine, more directly printing.

17, a kind of plate-making of lithographic plate and printing process, after wherein the original edition of lithographic printing plate described in the claim 11 being carried out image exposure by laser, be directly installed on the printing machine and print, carry out image exposure with laser after perhaps on being installed to printing machine, more directly printing.

Images