CN100522644C - Method of manufacturing lithographic printing plate support - Google Patents

Abstract

A method of manufacturing a lithographic printing plate support having a step of subjecting an aluminum plate to an electrochemical graining treatment in which alternating current is passed through the aluminum plate in an aqueous solution containing at least chloride ion and nitrate ion so that total amount of electricity when the aluminum plate serves as an anode is 100 to 300 C/dm<2>. By this method, a lithographic printing plate support which makes it possible to obtain a presensitized plate having both an excellent scumming resistance and a good press life by a single electrochemical graining treatment.

Description

The manufacture method of support body for lithographic plate printing plate

Technical field

The present invention relates to the manufacture method of support body for lithographic plate printing plate.At length say, relate to the manufacture method of the support body for lithographic plate printing plate that is used for all outstanding original edition of lithographic printing plate of stain resistance and anti-brush.

Background technology

Lithography is the mode of printing that has utilized water and oil at all not to mix, on the printing surface of the lithographic plate that is used to this, form the zone accepting water and repel the oiliness China ink (below, this zone is called " non-image portion ".), and repel water and accept the oiliness China ink the zone (below, this zone is called " image portion ".)。

Be used for lithographic plate the lithographic printing plate-use aluminum support (below, also be called " support body for lithographic plate printing plate " simply) the surface, require its hydrophily and water-retaining property fabulous owing to it is used to bear non-image, and require its adhesiveness to wait the various performances of reciprocity remarkably thereon with the image recording layer that forms.If the hydrophily on support body for lithographic plate printing plate surface is low excessively, printing ink can be attached on non-image when then printing, and the pollution that produces blanket cylinder, and then produce the so-called end and pollute.That is stain resistance variation.In addition, if the water-retaining property on surface is low excessively, do not increase damping water when then printing, it is improper that then generating unit is divided the obstruction etc. of shade.In addition, if low excessively with the adhesiveness of image recording layer, then image recording layer is easy to peel off, and durability (anti-brush) is poor for a long time for the printing number.

Therefore, improve, on the surface of support body for lithographic plate printing plate, carry out asperities processing and other surface treatment in order to make various performances such as stain resistance and anti-brush.As the method for asperities processing, known for example ball milling (ball graining), brushing (brush grainig), line mill (wiregraining), abrasive blasting mechanical asperities processing such as (b1ast graining), in acid solution the dipping aluminium sheet and on aluminium sheet, apply the processing of electrochemistry asperities, chemical attack (chemical asperities processing) of alternating current, with the method for their combinations.

In these asperities processing methods, when carrying out the processing of electrochemistry asperities,, then on whole of surface of aluminum plate, evenly form the recess (pit) of about 1～5 μ m of average diameter if use the aqueous solution contain nitric acid as acid solution.In addition, contain aqueous solution of hydrochloric acid as acid solution, then on whole of surface of aluminum plate, evenly to form the pit of about 0.01～0.5 μ m of average diameter if use.

In addition, after carrying out using the electrochemistry asperities processing of the aqueous solution contain nitric acid as acid solution, use the electrochemistry asperities processing that contains aqueous solution of hydrochloric acid if carry out as acid solution, then on the surface of aluminium sheet, spread all over pit stack concavo-convex that whole surface forms the pit of about 1～5 μ m of average diameter and about 0.01～0.5 μ m of average diameter.The lithographic plate of the aluminium sheet of this surface configuration as support body for lithographic plate printing plate, stain resistance and anti-brush are good.

In addition, in patent documentation 1, put down in writing the manufacture method about the offset printing roughing plate that comprises following operation, wherein, described operation has: in the solution that forms add nitric acid in 1～3% hydrochloric acid and surpassing 10A/dm ²Current density under aluminium sheet or aluminium alloy plate are carried out alternating current electrolysis and form the operation of asperities, in alkaline aqueous solution, carry out mildly corrosive operation and form the operation of the anodic oxidation diaphragm below the thick 5 μ m by carrying out anodized.

Patent documentation 1: special public clear 48-No. 28123 communiques

But, after carrying out using the electrochemistry asperities processing of the aqueous solution contain nitric acid as acid solution, carry out using when containing the electrochemistry asperities of aqueous solution of hydrochloric acid as acid solution, need carry out the processing of twice electrochemistry asperities.Therefore, many for making the needed operation of support body for lithographic plate printing plate, numerous and diverse operation increases.

In addition, the present inventor studies, the result as can be known, with regard to the technology of patent documentation 1 record, on the surface of aluminium sheet, mix the pit of about 1～5 μ m of formation average diameter and the thick recess that average diameter surpasses 10 μ m, the lithographic plate of the aluminium sheet of this surface configuration as support body for lithographic plate printing plate, its stain resistance and anti-brush are not enough.

Summary of the invention

Therefore, the objective of the invention is to, the manufacture method that can be obtained the support body for lithographic plate printing plate of all outstanding original edition of lithographic printing plate of stain resistance and anti-brush by the processing of primary electrochemical asperities is provided.

The inventor has carried out wholwe-hearted research in order to achieve the above object, found that in the aqueous solution that contains chloride ion and nitrate ion at least, and the electric weight summation when aluminium sheet being applied alternating current and make above-mentioned aluminium sheet be anode is 100～300C/dm ²The time, though the number of times of aluminium sheet being implemented the processing of electrochemistry asperities for once, uses the stain resistance and the anti-brush of original edition of lithographic printing plate of support body for lithographic plate printing plate of acquisition all outstanding.

That is, the invention provides following (1)～(5).

(1) manufacture method of support body for lithographic plate printing plate, it is in the aqueous solution that contains chloride ion and nitrate ion at least, the electric weight summation when aluminium sheet is applied alternating current and makes described aluminium sheet be anode is 100～300C/dm ², carry out the processing of electrochemistry asperities, obtain support body for lithographic plate printing plate, chloride ion concentration is 8～50g/L in the described aqueous solution, nitrate ion concentration is 0.8～6g/L.

(2) about the manufacture method of the support body for lithographic plate printing plate of record in above-mentioned (1), the above-mentioned aqueous solution contains hydrochloric acid and nitric acid.

(3) about the manufacture method of the support body for lithographic plate printing plate of any one record in above-mentioned (1)～(2), the pH of the above-mentioned aqueous solution is below 0.8.

(4) about the manufacture method of the support body for lithographic plate printing plate of any one record in above-mentioned (1)～(3), the above-mentioned aqueous solution contains the above aluminium ion of 2g/L.

(5) manufacture method of the support body for lithographic plate printing plate of any one record in above-mentioned (1)～(4), above-mentioned aluminium sheet has concavo-convex printed words from the teeth outwards.

As described above, according to the present invention, can obtain when forming plate printing plate, to be used for the support body for lithographic plate printing plate of all outstanding original edition of lithographic printing plate of stain resistance and anti-brush.In addition, when forming plate printing plate, be used for the support body for lithographic plate printing plate of all outstanding original edition of lithographic printing plate of stain resistance and anti-brush, can obtain by on aluminium sheet, implementing the processing of primary electrochemical asperities.

Description of drawings

Fig. 1 is an employed pattern sectional view of washing the device of processing by free-falling curtain shape liquid film during the washing in support body for lithographic plate printing plate manufacture method of the present invention is handled.

Fig. 2 is the pattern sectional view that expression has formed the overlapping rough aluminium sheet that forms of pit of the pit of average diameter 1～5 μ m and average diameter 0.01～0.5 μ m.

Fig. 3 is the curve map that is illustrated in an example of the employed AC wave shape of electrochemistry asperities processing in the support body for lithographic plate printing plate manufacture method of the present invention.

Fig. 4 is the skeleton diagram of an example of the radial mode groove in the electrochemistry asperities processing that exchanges that has been illustrated in use in the support body for lithographic plate printing plate manufacture method of the present invention.

Fig. 5 is the skeleton diagram of employed anodized device in the anodized in support body for lithographic plate printing plate manufacture method of the present invention.

Fig. 6 is the side view of the notion of mechanical asperities treatment process in the expression support body for lithographic plate printing plate manufacture method of the present invention.

Among the figure: 1-aluminium sheet, 2,4-roller shape brush, 3-grinding milk, 5,6,7,8-back up roll, 11-aluminium sheet, 12-radially drum-type rolls, 13a, 13b-main pole, 14-electrolytic treatments liquid, 15-electrolyte supply mouth, 16-slit, 17-electrolyte path, 18-impressed current anode, 19a, 19b-IGCT, 20-AC power, 40-main electrolytic cell, 50-impressed current anode groove, 100-device of processing, 102-water washed by free-falling curtain shape liquid film, 104-water tank, the 106-tube that supplies water, 108-rectification part, 410-anodized device, 412-power supply groove, 413-medial launder, 414-anodized groove, 416-aluminium sheet, 418,426-electrolyte, 420-anode, 422,428-deflector roll, 424-niproll, 430-negative electrode, 434-dc source, 436,438-feed flow nozzle, 440-shield, 442-leakage fluid dram.

The specific embodiment

Below, the present invention is described in detail.

[manufacture method of support body for lithographic plate printing plate]

＜aluminium sheet (aluminum) 〉

In the manufacture method of support body for lithographic plate printing plate of the present invention, can use known aluminium sheet.The aluminium sheet that the present invention uses is with the aluminium of the dimensionally stable metal as principal component, is made of aluminum or aluminum alloy.Except pure aluminum plate, can also use with aluminium as principal component and contain the alloy sheets of other element of trace.

In this manual, the above-mentioned various substrates that aluminum or aluminum alloy constituted being referred to as aluminium sheet uses.Other yuan that can contain in the above-mentioned aluminium alloy have silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium etc., and the content of other element is below the 10 quality % in the alloy.

Be used for aluminium sheet of the present invention like this, its composition is not particularly limited, for example can suitably utilize the 4th edition (nineteen ninety at Aluminium Handbook, the distribution of light metal association) material known in the past of record in, for example Al-Mn of JIS A1050, JIS A1100, JIS A1070, the JIS A3004 that contains Mn, international registration alloy 3103A etc. is an aluminium sheet.In addition, in order to increase hot strength, can also use the Al-Mg that has added the magnesium more than the 0.1 quality % in these aluminium alloys is that alloy, Al-Mn-Mg are alloy (JIS A3005).Have, can also use the Al-Zr that contains Zr, Si is that alloy or Al-Si are alloy again.In addition, also can use Al-Mg-Si is alloy.

Aluminum alloy rolled and the aluminium sheet that obtains of the UBC (Used BeverageCan) that can also use the aluminum beverage pot that dissolving is finished using is arranged again.

In this aluminium sheet, Cu content is preferably more than the 0.00 quality %, more preferably more than the 0.01 quality %, and more preferably more than the 0.02 quality %, in addition, below the preferred 0.15 quality %, more preferably below the 0.11 quality %, further below the preferred 0.03 quality %.Particularly preferably be the aluminium sheet that Si:0.07～0.09 quality %, Fe:0.20～0.29 quality %, Cu:0.03 quality % are following, Mn:0.01 quality % is following, Mg:0.01 quality % is following, Cr:0.01 quality % is following, Zn:0.01 quality % is following, Ti:0.02 quality % is following, Al:99.4 quality % is above.

Relevant JIS1050 material, the technology that is proposed by the applicant is documented in following each communique: the spy opens clear 59-No. 153861, the spy opens clear 61-No. 51395, the spy opens clear 62-No. 146694, the spy opens clear 60-No. 215725, the spy opens clear 60-No. 215726, the spy opens clear 60-No. 215727, the spy opens clear 60-No. 216728, the spy opens clear 61-No. 272367, the spy opens clear 58-No. 11759, the spy opens clear 58-No. 42493, the spy opens clear 58-No. 221254, the spy opens clear 62-No. 148295, No. 4-254545, Te Kaiping, No. 4-165041, Te Kaiping, special fair 3-No. 68939, No. 3-234594, Te Kaiping, No. 1-47545, special justice and spy open clear 62-No. 140894.In addition, knownly in special fair 1-No. 35910 communiques, special public clear 55-No. 28874 communiques etc., also put down in writing relevant technologies.

Relevant JIS1070 material, the technology that the applicant proposes is documented in following each communique: the spy opens flat 7-No. 81264, spy and opens flat 7-No. 305133, spy and open flat 8-No. 49034, spy and open flat 8-No. 73974, spy and open flat 8-No. 108659 and spy and open flat 8-No. 92679.

Relevant Al-Mg is an alloy, and the technology that the applicant proposes is documented in following each communique: special public clear 62-No. 5080, special public clear 63-No. 60823, special fair 3-No. 61753, the spy opens clear 60-No. 203496, the spy opens clear 60-No. 203497, special fair 3-No. 11635, the spy opens clear 61-No. 274993, the spy opens clear 62-No. 23794, the spy opens clear 63-No. 47347, the spy opens clear 63-No. 47348, the spy opens clear 63-No. 47349, the spy opens clear 64-No. 1293, the spy opens clear 63-No. 135294, the spy opens clear 63-No. 87288, special fair 4-No. 73392, special fair 7-No. 100844, the spy opens clear 62-No. 149856, special fair 4-No. 73394, the spy opens clear 62-No. 181191, special fair 5-No. 76530, the spy opens clear 63-No. 30294 and special fair 6-No. 37116.In addition, opening flat 2-No. 215599 communiques, spies the spy opens in clear 61-No. 201747 communiques etc. and has also put down in writing relevant technologies.

Relevant Al-Mn is an alloy, and the technology that the applicant proposes is documented in the spy and opens clear 60-No. 230951, spy and open flat 1-No. 306288 and spy and open in flat 2-No. 293189 each communiques.In addition, opening clear 61-No. 35995, spy special public clear 54-No. 42284, special fair 4-No. 19290, special fair 4-No. 19291, special fair 4-No. 19292, spy opens clear 64-No. 51992, spy and opens flat 4-No. 226394 each communique, United States Patent (USP) the 5th, 009, No. 722 specifications, United States Patent (USP) the 5th, also put down in writing relevant technologies in 028, No. 276 specification etc.

Relevant Al-Mn-Mg is an alloy, and the technology that the applicant proposes is documented in the spy and opens in clear 62-No. 86143 communiques and flat 3-No. 222796 communiques of Te Kai.In addition, opening clear 60-No. 63346, spy special public clear 63-No. 60824, spy opens clear 60-No. 63347, spy and opens flat 1-No. 293350 each communique, European patent the 223rd, No. 737, United States Patent (USP) the 4th, 818, No. 300, BP the 1st, also put down in writing relevant technologies in each specification of 222, No. 777 etc.

Relevant Al-Zr is an alloy, and the technology that the applicant proposes is documented in special public clear 63-No. 15978 communiques and clear 61-No. 51395 communiques of Te Kai.In addition, opening clear 63-No. 143234, spy the spy opens in each clear 63-No. 143235 communique etc. and has also put down in writing relevant technologies.

Relevant Al-Mg-Si is an alloy, in BP the 1st, 421, has put down in writing relevant technologies in No. 710 specifications etc.

Make aluminium alloy become sheet material, for example can adopt following method.At first, the molten aluminium alloy of the alloying component content that is adjusted to regulation is carried out purified treatment according to conventional method, and casting.When purified treatment, in order to remove not gas such as hydrogen in the motlten metal, implement following the processing: cosolvent is handled; Use the degassing of argon gas, chlorine etc. to handle; Use so-called hard medium filter such as earthenware filter, ceramic foam filter and with the filter as filtering material such as alumina wafer, alumina balls, and the filtration treatment of glass fiber filter; The perhaps processing of combination degassing processing and filtration treatment.

In order to prevent the defective that foreign matter caused such as non-metallic inclusion, oxide in the motlten metal, and be dissolved in the defective that gas caused in the motlten metal, preferably implement these purified treatment.The filtration treatment of relevant motlten metal is documented in following each communique: the spy opens flat 6-No. 57432, spy and opens flat 3-No. 162530, spy and open flat 5-No. 140659, spy and open flat 4-No. 231425, spy and open flat 4-No. 276031, spy and open flat 5-No. 311261, spy and open flat 6-No. 136466 etc.In addition, the degassing of relevant motlten metal is handled, and is documented in the spy and opens flat 5-No. 51659 communiques, real opening in flat 5-No. 49148 communiques etc.The applicant opens in flat 7-No. 40017 communiques the spy, has also provided the technology of the degassing of relevant motlten metal.

Then, use the motlten metal of implementing purified treatment as mentioned above to cast.Relevant casting method has with the method for the use solid template of DC casting representative and drives the method for template with the use of continuous casting process representative.

In DC casting, in being 0.5～30 ℃/second scope, cooling velocity solidifies.If 0.5 ℃/second of less than, the then thick intermetallic compound of a large amount of sometimes formation.When carrying out the DC casting, can make the ingot casting of thickness of slab 300～800mm.According to conventional method, this ingot casting is carried out flush cut as required, usually, the 1～30mm on cutting top layer, preferred 1～10mm.Before and after it, carry out evenly heating as required and handle.When carrying out the evenly heating processing,, under 450～620 ℃, carry out 1～48 hour heat treatment for fear of thickization of intermetallic compound.When heat treatment was lower than 1 hour, the effect that evenly heating is handled was insufficient sometimes.In addition, when not carrying out the evenly heating processing, the advantage that can reduce cost is arranged.

Afterwards, implement hot rolling, cold rolling and form the milled sheet of aluminium sheet.The beginning temperature of hot rolling be 350～500 ℃ more suitable.Before or after hot rolling, perhaps it also can be implemented intermediate annealing and handle midway.The condition that intermediate annealing is handled is: use periodic annealing furnace to heat 2～20 hours down at 280～600 ℃, preferably heated 2～10 hours down at 350～500 ℃, perhaps use continuous annealing furnace, heat down below 6 minutes, preferably heat below 2 minutes down at 450～550 ℃ at 400～600 ℃.Heat with the programming rate of continuous annealing furnace, crystalline structure is attenuated with 10～200 ℃/second.

By above operation, be finish-machined to the specific thickness aluminium sheet of 0.1～0.5mm for example, can also further improve flatness by apparatus for correcting such as roll leveller, tension level(l)ers.The improvement of flatness also can be cut into aluminium sheet the laggard row of sheet, but in order to enhance productivity, preferably carries out under continuous coiled material state.In addition, wide for the plate that is processed into regulation, can also make aluminium sheet pass through slitter line.Have again,, also thin oil film can be set on the surface of aluminium sheet in order to prevent the scratch that friction produced between the aluminium sheet.Can suitably use volatile material or and nonvolatile matter as required as oil film.

On the other hand, as continuous casting process, industrial enforcement be the method for the use chill roll of double roller therapy (Hunter method), 3C method representative, two-tape method (Hazelette method), the ア Le ス イ ス キ ャ ス -use salband of II type representative and the method for cooling block.When using continuous casting process, in being 100～1000 ℃/second scope, cooling velocity solidifies.Continuous casting process is faster than DC casting cooling velocity usually, therefore has the feature that can improve with respect to the alloying component solid solubility of aluminum substrate.Relevant continuous casting process, the technology that the applicant proposes is documented in following each communique: the spy opens flat 3-No. 79798, spy and opens flat 5-No. 201166, spy and open flat 5-No. 156414, spy and open flat 6-No. 262203, spy and open flat 6-No. 122949, spy and open flat 6-No. 210406, spy and open flat 6-No. 26308 etc.

When casting continuously,, can be directly the cast sheet of thickness of slab 1～10mm be cast continuously, obtained to omit the advantage of hot-rolled process if for example use Hunter method etc. to adopt the method for chill roll.In addition, when using Hazelette method etc. to adopt the method for salband, the cast sheet that can cast thickness of slab 10～50mm disposes hot roll usually at once and is rolled continuously after casting, can obtain the continuous casting milled sheet of thickness of slab 1～10mm thus.

These continuous castings milled sheets and DC casting explanation similarly through the improvement of cold rolling, intermediate annealing, flatness, operation such as cut, be finish-machined to thickness of slab into for example 0.1～0.5mm.Intermediate annealing condition and cold rolling condition during relevant use continuous casting process, the technology that the applicant proposed are documented in the spy and open flat 6-No. 220593, spy and open flat 6-No. 210308, spy and open flat 7-No. 54111, spy and open in each communique etc. of flat 8-No. 92709.

Aluminium sheet used in the present invention preferably carries out the modifier treatment of the H18 of JIS defined.

As the aluminium sheet of such manufacturing, wish to have the various characteristics of the following stated.

In order to obtain as the necessary stiffness of support body for lithographic plate printing plate, preferred 0.2% proof stress of the intensity of aluminium sheet is more than the 120MPa.Have, required stiffness to a certain degree when handling in order to obtain to carry out burning (burning) is more than the 80MPa in 0.2% proof stress of 270 ℃ of heat treated after 3～10 minutes preferably, more preferably more than the 100MPa again.When to aluminium sheet special requirement stiffness, can adopt the aluminum that has added Mg, Mn, when making stiffness too strong, aluminium sheet therefore should be according to purposes to the easy suitability variation of the plate cylinder of printing machine, the suitable addition of selecting material and micro constitutent.About these, the relevant technologies that the applicant proposes is documented in the spy and opens flat 7-No. 126820 communiques, spies and open in clear 62-No. 140894 communiques etc.

In addition, aluminium sheet more preferably tensile strength be 160 ± 15N/mm ², 0.2% proof stress is that the percentage elongation of 140 ± 15MPa, JIS Z2241 and Z2201 defined is 1～10%.

When carrying out chemical asperities processing and the processing of electrochemistry asperities, the crystalline structure of surface of aluminum plate might become the bad reason of generating plane matter, so the crystalline structure of aluminium sheet is preferably too not thick on the surface.Below the wide preferred 200 μ m of the crystalline structure of surface of aluminum plate, more preferably below the 100 μ m, further below the preferred 50 μ m, in addition, below the preferred 5000 μ m of the length of crystalline structure, more preferably below the 1000 μ m, further below the preferred 500 μ m.About these, the relevant technologies that the applicant proposes is documented in the spy and opens flat 6-No. 218495, spy and open flat 7-No. 39906, spy and open in flat 7-No. 124609 each communiques etc.

When the asperities processing of carrying out chemistry and electrochemical asperities processing, the uneven distribution of the alloying component of surface of aluminum plate might cause the generation that face matter is bad, so the distribution of the alloying component of aluminium sheet preferably avoids not too even from the teeth outwards.About these, the relevant technologies that the applicant proposes is documented in the spy and opens flat 6-No. 48058, spy and open flat 5-No. 301478, spy and open in flat 7-No. 132689 each communiques etc.

About the intermetallic compound of aluminium sheet, the size of its intermetallic compound and density exert an influence to chemical asperities processing and the processing of electrochemistry asperities sometimes.About these, the relevant technologies that the applicant proposes is documented in the spy and opens flat 7-No. 138687, spy and open in flat 4-No. 254545 each communiques etc.

Among the present invention, also can the aluminium sheet shown in as mentioned above is rolling by punching press in its final rolling process etc., transfer printing etc. forms concavo-convex back and use.

Wherein, preferable methods is: and be adjusted to the cold rolling of final thickness of slab, perhaps together cold rolling with the fine finishining of the adjusted surface configuration of the final thickness of slab of fine finishining, make male and fomale(M﹠F) be crimped on transfer printing concaveconvex shape on the aluminium sheet, make the surface of aluminium sheet form concavo-convex printed words.Specifically can be suitable for the spy and open the method for putting down in writing in flat 6-No. 262203 communiques.

By using the surface to have the aluminium sheet of concavo-convex printed words, can obtain average headway and the uniform concavo-convex printed words of the degree of depth by the concavo-convex printed words that form by brush and grinding agent, thereby improve stain resistance.In addition, can reduce the energy of being consumed in the caustic corrosion processing of back and the asperities processing, make the adjustment of the amount of damping water on the printing machine become easy simultaneously.For example, in the 1st corrosion treatment described later, can make etching extent be reduced to about 3g/m ²Below.In addition, if use the aluminium sheet with concavo-convex printed words, the surface area of the support body for lithographic plate printing plate of acquisition increases, so anti-brush is outstanding.

Carry out in the final cold rolling process of transfer printing particularly preferably in common aluminium sheet.Rolling preferred usefulness 1～3 circulation that is used for transfer printing is carried out, and divides other reduction ratio preferred 3～8%.

In addition, by concavo-convex more preferably giving on two faces of aluminium sheet that transfer printing gave.Therefore, owing to the percentage elongation of the surface and the aluminium sheet at the back side can be adjusted into same degree, so can obtain the good aluminium sheet of flatness.

Have the method for concavo-convex rolling cylinder (below, be also referred to as transfer platen) as the surface that obtains to be used for concavo-convex transfer printing, for example can enumerate gunite, electrolysis, laser method, discharge processing method, make up their method.Wherein, the method for preferred compositions gunite and electrolysis.In gunite, also preferred air-jet method.

Preferred 1～the 10kgf/cm of air pressure in the air-jet method ²(9.81 * 10 ⁴～9.81 * 10 ⁵Pa), more preferably 2～5kgf/cm ²(1.96 * 10 ⁵～4.90 * 10 ⁵Pa).

The employed sand grains of air-jet method is not particularly limited so long as the aluminium oxide particles of regulation particle diameter is just passable.When sand grains uses hard and each angle particle when being the aluminium oxide particles of acute angle, make the surface of transfer platen form dark and concavo-convex uniformly easily.

The average grain diameter of aluminium oxide particles is 50～150 μ m, preferred 60～130 μ m, more preferably 70～90 μ m.If be above-mentioned scope, can obtain as the enough big surface roughness of transfer platen, thereby use this transfer platen and the surface roughness of having given concavo-convex aluminium sheet becomes enough big.And, can make the pit number also become abundant.

In air-jet method, preferably spray 2～5 times, wherein more preferably carry out 2 times.When carrying out spraying for 2 times, spray formed concavo-convex irregular protuberance at the 1st time and can prune, so the rolling cylinder that obtains in use and having given on the surface of concavo-convex aluminium sheet is not easy to form local dark recess by the 2nd time injection.Its result, the development of lithographic plate (sensitivity) becomes outstanding.

Jet angle in the air-jet method is preferably 60～120 ° with respect to jet face (cylinder surface), more preferably 80～100 °.

After carrying out air-jet method, carry out preferably grinding up to average surface roughness (R before plating described later handles _a) value after jet descends till 10～40%.Grind preferred sand paper, grinding stone or the polishing wheel of using.By grinding transfer platen surface protuberance height is become neatly, its result uses this transfer platen to be paid concavo-convex surface of aluminum plate and is difficult to form local dark concave portion.Thereby the development of lithographic plate (sensitivity) becomes good.

Preferred 0.4～1.0 μ m of the mean roughness on transfer platen surface (Ra), more preferably 0.6～0.9 μ m.

Preferred 1000～40000/mm of the mountain number on transfer platen surface ², more preferably 2000～10000/mm ²If the mountain number is very little, the water-retaining property of support body for lithographic plate printing plate and and the adhesiveness variation of image recording layer.If water-retaining property is relatively poor, when becoming lithographic plate, the site part is polluted easily.

Material to transfer platen is not particularly limited, and for example can use known rolling cylinder material.

The preferred cylinder that uses steel among the present invention.The wherein preferred cylinder of making by casting.The example that preferred cylinder material is formed is that C:0.07～6 quality %, Si:0.2～1 quality %, Mn:0.15～1 quality %, P:0.03 quality % are following, S:0.03 quality % is following, Cr:2.5～12 quality %, Mo:0.05～1.1 quality %, Cu:0.5 quality % are following, V:0.5 quality % is following, remainder: iron and inevitable impurity.

In addition, can also list the tool steel (SKD), high-speed steel (SKH), the high-carbon-chromium bearing steel (SUJ) that usually use as rolling cylinder, contain carbon and chromium and molybdenum and vanadium forged steel as alloying element.In order to obtain the long cylinder life-span, can use the high-chromium alloy cast-iron that contains 10～20 quality % chromium of having an appointment.

Wherein, the preferred cylinder of making by casting that uses.At this moment, the hardness after quenching, the tempering is by Hs preferred 80～100.Lonneal is preferably carried out in tempering.

Preferred 200～the 1000mm of the diameter of cylinder.In addition, the preferred 1000～4000mm of the face length of cylinder.

After air-jet method etc. has formed concavo-convex transfer platen and cleaning, preferably implement hard processing such as quenching, hard chrome plating.Can improve abrasion performance, life-saving thus.

The preferred especially hard chrome plating of hard processing.About hard chrome plating, can adopt well-known in the past as industrial hard chrome plating method by having used CrO ₃-SO ₄Bath, CrO ₃-SO ₄The electric plating method of-fluoride bath etc.

Preferred 5～15 μ m of the thickness of hard chrome plating film.If be above-mentioned scope, the effect of improving of abrasion performance becomes abundant.The thickness of hard chrome plating film can be regulated by adjusting the electroplating processes time.

Before hard chrome plating, preferably be used for chromed hardened electroplate liquid, cylinder as anode, is used DC current, at 5000～50000C/dm ²Carry out electrolytic treatments under the electric weight.Thus, can make the concavo-convex homogenising of cylinder surface.

In aluminium sheet, surface average roughness R _aMeasuring method be the mensuration of carrying out two-dimentional roughness with contact pin type fineness gauge (for example sufcom575, Tokyo Micronics Inc. system), measure the mean roughness R of 5 ISO4287 defineds _a, its mean value is defined as mean roughness.

Show the condition determination of two-dimentional roughness below.

＜condition determination 〉

Cutoff (cut off value) 0.8mm, correction for inclined FLAT-ML, measured length 3mm, 10000 times of longitudinal magnifications, sweep speed 0.3mm/sec, contact pilotage point diameter 2 μ m

Also has R _MaxAnd R _SmCan measure according to ISO4287.

The aluminium sheet that the present invention uses is continuous banded sheet material or sheet material.That is, can be reel aluminium sheet (aluminium web), also can be cropped one-tenth and thin slice as the sheet-fed shape of corresponding size of original edition of lithographic printing plate of product export etc.

The scar of surface of aluminum plate might become defective when being processed into support body for lithographic plate printing plate, therefore, in the stage before making the surface treatment procedure of support body for lithographic plate printing plate, need control the generation of scar as much as possible.So preferably be not easy abrasive container dimensions with stable morphology and when carrying.

Under the situation of reel aluminium sheet, container dimensions as aluminium, for example on iron supporting plate, spread hardboard and felt, lay the corrugated paper ring flat-plate at the product two ends, (poly tube) will all wrap with the poly property management, insert wooden ring to coiled material internal diameter position, put felt at the peripheral part of coiled material, tighten with banded iron, and show at its peripheral part.In addition, packaging material can use polyethylene film, and padded coaming uses needle punched felt, hardboard.Other also has various forms, so long as can abrasive method when stable and transportation just impassable, be not particularly limited.

The thick of the aluminium sheet that the present invention uses is about 0.1mm～0.6mm, preferred 0.15mm～0.4mm, more preferably 0.2mm～0.3mm.The change that this thickness can suit according to the size of printing machine, the size of galley and user's hope etc.

＜surface treatment 〉

The present invention is in the aqueous solution that contains chloride ion and nitrate ion at least, and the electric weight summation when above-mentioned aluminium sheet is applied alternating current and makes above-mentioned aluminium sheet be anode is 100～300C/dm ², carry out the processing of electrochemistry asperities, obtain support body for lithographic plate printing plate.

Also have, in surface treatment, also can comprise electrochemistry asperities processing various operations in addition.

Specifically, can suitably enumerate the method that (below be also referred to as " the 1st abatement processes "), the processing of electrochemistry asperities, the corrosion treatment in aqueous alkali (below be also referred to as " the 2nd corrosion treatment "), the abatement processes in acidic aqueous solution (below be also referred to as " the 2nd abatement processes "), anodized are handled in the corrosion treatment for example carried out in order in aqueous alkali (below be also referred to as " the 1st corrosion treatment "), the scrubbing in acidic aqueous solution (desmut).

In addition, after above-mentioned anodized, also further preferably carry out the method for sealing of hole processing, hydrophilicity-imparting treatment or sealing of hole processing and hydrophilicity-imparting treatment thereafter.

In addition, before the 1st corrosion treatment, also can carry out mechanical asperities processing.As mechanical asperities processing, for example can use with metal wire scratch the aluminium surface line-brushing method, with mill ball and grinding agent to the aluminium surface carry out graining ball-milling method, the spy open put down in writing in flat 6-No. 135175 communiques and special public clear 50-No. 40047 communiques the surface is carried out the brushing method of graining with nylon bruss and grinding agent.

In addition, as mentioned above, also can use male and fomale(M﹠F) with transfer platen to be crimped on printing transferring method (transfer platen method) on the aluminium sheet.Promptly, open clear 60-No. 36195, spy and open the method for putting down in writing in clear 60-No. 203496 each communiques except open clear 55-No. 74898, spy the spy, also can use with the spy who carries out being transferred as for several times feature and open flat 6-No. 55871 communiques, be that elasticity is that the spy of feature opens the method for putting down in writing in flat 6-No. 24168 communiques with the surface.

Wherein, because the transfer platen method is easy to adapt to the high speed of the manufacturing process of support body for lithographic plate printing plate, so preferred.The transfer platen method preferably becomes the cold rolling of final thickness of slab or the adjusted surface configuration of final thickness of slab is carried out accurately machined fine finishining and carry out transfer printing in cold rolling in adjustment as mentioned above.

By before the 1st corrosion treatment, carrying out mechanical asperities processing or giving, can reduce the electric weight that is used for the processing of electrochemistry asperities by the concavo-convex of transfer platen.In addition, by before the 1st corrosion treatment, carrying out mechanical asperities processing or give, can improve luminous (shiny) (the observing easy degree of the shinny state of the space of a whole page) of using the lithographic plate that the support body for lithographic plate printing plate that obtains makes by the concavo-convex of transfer platen.

Below, each operation of surface-treated is elaborated.

＜the 1 corrosion treatment 〉

It is by making above-mentioned aluminium sheet contact the processing of dissolving the top layer with aqueous slkali that caustic corrosion is handled.

The 1st corrosion treatment of carrying out before the processing of electrochemistry asperities its objective is by the processing of electrochemistry asperities to form uniform recess, and removes the surperficial ROLLING OIL of aluminium sheet (aluminum), dirt, autoxidation tunicle etc.

In the 1st corrosion treatment, carry out the preferred 0.5g/m of etching extent on the surface of electrochemistry asperities processing later on ²More than, more preferably 1g/m ²More than, in addition, preferred 10g/m ²Below, more preferably 5g/m ²Below.If etching extent is 0.5g/m ²More than, can in the processing of electrochemistry asperities, make it generate uniform pit.If etching extent is 10g/m ²Below, then the use amount of aqueous alkali tails off, and is favourable economically.

The etching extent at the back side that carries out the face of electrochemistry asperities processing preferably carries out more than 5% of etching extent of the face of electrochemistry asperities processing, and is more preferably more than 10%, preferred below 50% in addition, more preferably below 30%.If in above-mentioned scope, then remove the effect of ROLLING OIL at the aluminium sheet back side and outstanding with the balance of economy.

Even in the 2nd corrosion treatment described later, also be identical.

As the alkali that is used for aqueous slkali, can enumerate for example caustic alkali, alkali metal salt.Particularly, as caustic alkali, for example can enumerate: caustic soda, caustic potash.In addition, as alkali metal salt, for example can enumerate: alkali silicates such as sodium metasilicate, sodium metasilicate, positive potassium silicate, potassium silicate; Alkali carbonate such as sodium carbonate, potash; Alkali metal aluminate such as sodium aluminate, potassium aluminate; Alkali metal such as gluconic acid sodium salt, K-IAO glycuronate; Alkali metal hydrogen phosphates such as sodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate.Wherein, consider the solution of preferred caustic alkali and contain caustic alkali and the solution of alkali metal aluminate from the fast and cheap aspect of corrosion rate.The aqueous solution of preferred especially caustic soda.

In the 1st corrosion treatment, more than the preferred 1 quality % of the concentration of aqueous slkali, more preferably more than the 20 quality %, in addition, below the preferred 40 quality %, more preferably below the 35 quality %.

In addition, aqueous slkali preferably contains aluminium ion.More than the preferred 0.5 quality % of aluminium ion concentration, more preferably more than the 4 quality %, in addition, below the preferred 10 quality %, more preferably below the 8 quality %.Aforesaid aqueous slkali, for example, can water and the caustic soda aqueous solution and the sodium aluminate of 48 quality % modulate.

In the 1st corrosion treatment, the temperature of aqueous slkali is preferred more than 25 ℃, and is more preferably more than 40 ℃, preferred below 95 ℃ in addition, more preferably below 80 ℃.

In the 1st corrosion treatment, the processing time is preferred more than 1 second, and is more preferably more than 2 seconds, preferred below 30 seconds in addition, more preferably below 10 seconds.

When aluminium sheet was carried out corrosion treatment continuously, the aluminium ion concentration in the aqueous slkali rose, the etching extent change of aluminium sheet.Therefore, the management of the composition of corrosive liquid is best carries out according to following method.

Promptly, make the matrix of, electrical conductivity corresponding and proportion and temperature in advance with the matrix (matrix) of caustic soda concentration and aluminium ion concentration, or the matrix of electrical conductivity and ultrasonic propagation velocity and temperature, according to electrical conductivity and proportion and temperature, or electrical conductivity and ultrasonic propagation velocity and temperature measuring liquid composition, add caustic soda and water so that liquid consists of the control desired value.Then, overflow from circulating tank, make this amount of liquid keep constant by making corrosive liquid because of adding caustic soda and water and increasing.As the caustic soda that adds, can use the material of 40～60 industrial quality %.

As conductivity meter and densimeter, the meter of temperature-compensating is passed through in preferred use respectively.Preferably use differential pressure type as densimeter.

As the method that aluminium sheet is contacted with aqueous slkali, can enumerate for example make aluminium sheet by the method in the groove that aqueous slkali is housed, aluminium sheet is immersed in be equipped with method in the groove of aqueous slkali, aqueous slkali is sprayed on the method for surface of aluminum plate.

Wherein, preferably aqueous slkali is sprayed on the method for surface of aluminum plate.Particularly, have the playpipe in Φ 2～5mm hole from spacing with 10～50mm, more satisfactory with the method for the amount spraying corrosive liquid of per 1 playpipe 10～100L/min.Playpipe is preferably set to many.

After the caustic corrosion processing finishes, preferably use niproll (nip roller) to carry out mangle, and then after carrying out washing in 1～10 second, further carry out mangle with niproll.

Washing is handled, and the device that preferred use is washed processing by the liquid film that freely falls the curtain shape is washed, and washes with playpipe then.

Fig. 1 is a mode sectional drawing of washing the device of processing by the liquid film that freely falls the curtain shape.As shown in Figure 1, wash the device 100 of processing by the liquid film that freely falls the curtain shape, having storage stays the water tank 104 of water 102 and gives water drum 106 and the liquid film that freely falls the curtain shape is supplied with the rectification part 108 of aluminium sheet 1 from water tank 104 to what water tank 104 supplied water.

In device 100, water 102 when water 102 overflows from giving water pot 104, carries out rectification through rectification part by giving water drum 106 to providing for water pot 104, and the liquid film that freely falls the curtain shape is provided for aluminium sheet 1.During operative installations 100, the preferred 10～100L/min of liquid measure.In addition, the water 102 between device 100 and the aluminium sheet 1 is as the preferred 20～50mm of distance L of the liquid film existence that freely falls the curtain shape.Preferred 30～80 ° with respect to horizontal direction of the angle [alpha] of aluminium sheet are arranged again.

When using the liquid film that passes through free-falling curtain shape shown in Figure 1 to wash the device of processing, can implement washing equably to aluminium sheet and handle, therefore can improve the uniformity of the processing of being carried out before washing is handled.

As washing the device of processing, can suitably be exemplified as and be documented in the spy and open the device in the communique 2003-No. 96584 by the liquid film of free-falling curtain shape.

In addition, handle employed playpipe as washing, can use for example has a plurality of injection waters to diffuse into the playpipe of fan-shaped injection sheet on the width of aluminium sheet.Spray the preferred 20～100mm in interval of sheet, in addition, per 1 preferred 0.5～20L/min of liquid measure that sprays sheet.Playpipe preferably uses many.

＜the 1 abatement processes 〉

After carrying out the 1st corrosion treatment,, preferably implement pickling (the 1st abatement processes) for the pollution (dirt) of removing remained on surface.Abatement processes is undertaken by aluminium sheet is contacted with the aqueous solution.

The acid of using can be enumerated for example nitric acid, sulfuric acid, phosphoric acid, chromic acid.Wherein, preferred nitric acid, sulfuric acid.Specifically, can suitably use the waste liquid of the aqueous sulfuric acid that for example in anodized operation described later, uses.

In the management of the composition of abatement processes liquid, arbitrary method below can selecting to use: use corresponding to the electrical conductivity of the matrix of acid solution concentration and aluminium ion concentration and the method that temperature is managed; The method of managing with electrical conductivity and proportion and temperature; And the method for managing with electrical conductivity and hyperacoustic spread speed and temperature.

In the 1st abatement processes, the preferred use contained the acid of 0.5～30 quality % and the aluminum ions acid solution of 0.5～10 quality %.

The temperature of acid solution is preferred more than 25 ℃, and is preferred in addition below 95 ℃.

In the 1st abatement processes, the processing time is preferred more than 1 second, and is more preferably more than 2 seconds, preferred in addition below 30 seconds, more preferably below 10 seconds.

As the method that aluminium sheet is contacted with acid solution, can enumerate for example make aluminium sheet by the method in the groove that acid solution is housed, aluminium sheet is immersed in be equipped with method in the groove of acid solution, acid solution is sprayed on the method for surface of aluminum plate.

Wherein, preferably acid solution is sprayed on the method for surface of aluminum plate.Particularly, from having the playpipe in Φ 2～5mm hole at interval with 10～50mm, more satisfactory with the method for the amount spraying corrosive liquid of per 1 playpipe 10～100L/min.Playpipe is preferably set to many.

Abatement processes is preferably carried out mangle with niproll after finishing, and then after the washing of carrying out for 1～10 second is handled, carries out mangle with niproll.

It is identical with the washing processing after the caustic corrosion that washing is handled.But, per 1 preferred 1～20L/min of liquid measure that sprays sheet.

＜electrochemistry asperities processing 〉

With regard to the processing of electrochemistry asperities, it is in the aqueous solution that contains chloride ion and nitrate ion, and the electric weight summation when aluminium sheet is applied alternating current and makes aluminium sheet be anode is 100～300C/dm ²

According to electrochemistry asperities of the present invention processing, as shown in Figure 2, can obtain the aluminium sheet of the surface configuration that the pit of the recess (pit) of average diameter 1～5 μ m and average diameter 0.01～0.5 μ m superposes by the processing of primary electrochemical asperities.So, in the present invention, on the surface after the processing of electrochemistry asperities, owing to evenly form pit, so the anti-brush when forming lithographic plate is outstanding, in addition, because pit is even, so the stain resistance when forming lithographic plate is outstanding.

In electrochemistry asperities of the present invention processing, the electric weight summation when aluminium sheet is anode is 100～300C/dm ², preferred 150～250C/dm ²Electric weight summation when aluminium sheet is anode forms the pit of average diameter 1～5 μ m and even superpose concavo-convex of pit of average diameter 0.01～0.5 μ m if above-mentioned scope then can advance to implement the processing of sufficient electrochemistry asperities to aluminium sheet on the surface of aluminium sheet.In addition, the pit depth of average diameter 0.01～0.5 μ m compares a little with following that some is shallow, after promptly in containing the aqueous solution of nitric acid, aluminium sheet being applied alternating current and implement the electrochemistry asperitiesization, in containing aqueous solution of hydrochloric acid, it is applied the situation that alternating current is implemented the electrochemistry asperitiesization.

On the other hand, even use the aqueous solution that contains chloride ion and nitrate ion, if electric weight is many as the method for record in the patent documentation 1, then also can form thick pit everywhere in surface of aluminum plate, the pit that forms in surface of aluminum plate becomes inhomogeneous.

As the preferred 3～60g/L of concentration of the chloride ion of the aqueous solution of electrolyte, more preferably 8～50g/L.If in above-mentioned scope, then the uniformity of pit uprises.

In addition, as the preferred 0.5～20g/L of nitrate ion concentration, more preferably 0.8～6g/L.If in above-mentioned scope, then the uniformity of pit uprises.

Chloride ion is contained in the aqueous solution it by using hydrochloric acid as the raw material of the aqueous solution.In addition, also can use chlorides such as aluminium chloride, sodium chloride, ammonium chloride.Wherein preferably use aluminium chloride.Among the present invention, preferably use hydrochloric acid and chloride, more preferably use hydrochloric acid and aluminium chloride.When using hydrochloric acid, the preferred 3～30g/L of concentration of hydrochloric acid, more preferably 4～20g/L, further preferred 5～18g/L.

Nitrate ion is contained in the aqueous solution it by using nitric acid as the raw material of the aqueous solution.In addition, also can use nitrate such as aluminum nitrate, sodium nitrate, ammonium nitrate.When using nitric acid, the preferred 0.5～15g/L of concentration of nitric acid, more preferably 1～10g/L.

By making the aqueous solution that is used as electrolyte contain nitrate ion, can form the pit of average diameter 1～5 μ m in surface of aluminum plate, and, can form the pit of average diameter 0.01～0.5 μ m in surface of aluminum plate by making it contain chloride ion.Therefore, when the aqueous solution does not contain nitrate ion or chloride ion, can not obtain the aluminium sheet of surface configuration of the pit mutual superposition of the pit of average diameter 1～5 μ m and average diameter 0.01～0.5 μ m.

In addition, the preferred pH of the aqueous solution as electrolyte is below 0.8.By pH is below 0.8, and the uniformity of pit becomes higher.

The aqueous solution as electrolyte also can contain sulfuric acid.

In addition, the aqueous solution can also contain the sulphate that aluminum sulfate, sodium phosphate, ammonium sulfate etc. have sulfate ion except containing the sulfuric acid.

In addition, also can contain the compound that forms complex compound with copper according to the ratio of 1～200g/L.In mixed aqueous solution, also can dissolved iron, copper, manganese, nickel, titanium, magnesium, silicon etc. is contained in the element that contains in the aluminium alloy.Also can make its hypochlorous acid that contains 1～100g/L or hydrogen peroxide.

Aluminium ion concentration in the aqueous solution is preferably more than the 2g/L, more preferably 3～30g/L, further preferred 3～20g/L, further preferred 4～18g/L.If in above-mentioned scope, then the uniformity of pit uprises.In addition, can avoid the magnitude of recruitment of the aqueous solution to become too much.

Aluminium ion in the aqueous solution can contain by aluminium salt is dissolved in the aqueous solution.As aluminium salt, can use aluminium chloride, aluminum nitrate, aluminum sulfate etc., wherein, from the viewpoint that the shape of pit becomes good, the preferred use is included in the chloride ion that contains in the aqueous solution or the aluminium chloride or the aluminum nitrate of nitrate ion.

The control of the concentration of each composition of electrolyte is preferred and carry out with multicomponent measurement of concetration method such as concentration measuring method and FEEDFORWARD CONTROL and FEEDBACK CONTROL.Thus, can realize electrolyte concentration management accurately.

Multicomponent measurement of concetration method can, can enumerate method, neutralization titration, capillary electrophoresis analysis method, isotachophoresis (isotachophoresis, tubule formula isotachophoresis) analytic approach, the chromatography of ions that electrical conductivity (conductance) C that for example utilizes hyperacoustic spread speed and electrolyte in the electrolyte measures concentration.

The chromatography of ions is divided into the absorbance detection chromatography of ions, the non-inhibition type electric conductivity detection chromatography of ions, the inhibition type chromatography of ions etc. according to the kind of detector.Wherein, just can guarantee to measure stability, the preferably inhibition type chromatography of ions.

Current density in the processing of electrochemistry asperities is with regard to the preferred 10～300A/dm of the crest of current value ², more preferably 15～200A/dm ², further preferred 20～125A/dm ²If be 10A/dm ²More than, then production efficiency becomes better.If be 300A/dm ²Below, then because voltage is not high, it is excessive that power supply capacity can not become, so can reduce the power supply cost.

The processing of electrochemistry asperities can be used the electrochemical surface roughening method (electrolytic surface roughening method) that for example is documented in special public clear 48-No. 28123 communiques and the 896th, No. 563 specification of BP.

Relevant have various motions, can use United States Patent (USP) the 4th, 203, No. 637 specifications, spies open clear 56-No. 123400, spy and open clear 57-No. 59770, spy and open clear 53-No. 12738, spy and open clear 53-No. 32821, spy and open clear 53-No. 32822, spy and open clear 53-No. 32823, spy and open clear 55-No. 122896, spy and open clear 55-No. 132884, spy and open clear 62-No. 127500, spy and open flat 1-No. 52100, spy and open flat 1-No. 52098, spy and open clear 60-No. 67700, spy and open flat 1-No. 230800, spy and open described in each communique etc. of flat 3-No. 257199.

In addition, can also use the spy to open clear 52-No. 58602, the spy opens clear 52-No. 152302, the spy opens clear 53-No. 12738, the spy opens clear 53-No. 12739, the spy opens clear 53-No. 32821, the spy opens clear 53-No. 32822, the spy opens clear 53-No. 32833, the spy opens clear 53-No. 32824, the spy opens clear 53-No. 32825, the spy opens clear 54-No. 85802, the spy opens clear 55-No. 122896, the spy opens clear 55-No. 132884, the spy opens clear 48-No. 28123, special public clear 51-No. 7081, the spy opens clear 52-No. 133838, the spy opens clear 52-No. 133840, the spy opens clear 52-No. 133844, the spy opens clear 52-No. 133845, the spy opens clear 53-No. 149135, the spy opens described in each clear 54-No. 146234 communique etc.

Have again, add and Cu might form when using behind the compound of complex compound,, also can carry out uniform graining for the aluminium sheet that contains more Cu.As forming the compound of complex compound, can enumerate for example ammonia with Cu; The amine that the hydrogen atom of methylamine, ethamine, dimethylamine, diethylamine, trimethylamine, cyclohexylamine, triethanolamine, triisopropanolamine, EDTA ammonia such as (EDTAs) is obtained by alkyl replacements such as (aliphatic, aromatic series etc.); Metal carbonate classes such as sodium carbonate, potash, saleratus.Can also enumerate ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium carbonate in addition.

The temperature of mixed aqueous solution is preferred more than 20 ℃, and is more preferably more than 25 ℃, further preferred more than 30 ℃, preferred below 60 ℃ in addition, more preferably below 50 ℃, further preferred below 40 ℃.If be more than 20 ℃, the refrigerator operating cost that then is used to cool off can not uprise, and in addition, can control the phreatic use amount that is used to cool off.If be below 60 ℃, then be easy to guarantee the corrosion resistance of equipment.

The employed AC power ripple of electrochemical asperities processing is not particularly limited, and can use sine wave, square wave, trapezoidal wave, triangular wave etc.

Frequency is preferably 10～200Hz, more preferably 20～150Hz, further preferred 50～60Hz.If be more than the 10Hz, be difficult to produce the bigger pit of then planar (the square shape that the angle is arranged), it is better that stain resistance becomes.If be below the 200Hz, then be difficult to be subjected to the influence of the circuit inductance composition that Faradaic current flows through, be easy to make jumbo power supply.

Also have, so-called trapezoidal wave is meant the waveform shown in Fig. 3.Electric current is from 0 time to peaking (TP) preferred 0.3～2.0msec, more preferably 0.5～0.8msec in this trapezoidal wave.If be more than the 0.3msec, power making cost step-down then.If be below the 2msec, then the uniformity of pit becomes better.In addition, in triangular wave, can set arbitrarily current rise time.

In addition, as supply unit, can use the supply unit, the transformer that for example use commercial ac power to control power supply etc.Wherein, use the transformer control power supply of IGBT (Insulated Gate Bipolar Transistor) element to make it produce waveform arbitrarily by PWM (Pulse Width Modulation) control, change voltage with respect to the change in concentration of each composition in wide and thick, the electrolyte of aluminium sheet etc., when current value (current density of aluminium sheet) being controlled when constant, from the fabulous viewpoint of tracing property, preferred.

Fig. 4 is the skeleton diagram of an example that use, the radial mode groove in the electrochemical asperities processing that use to exchange in the manufacture method of expression support body for lithographic plate printing plate of the present invention.

Can connect the AC power more than 1 in the electrolytic cell.Control is applied to the current ratio of the anode and the negative electrode of the interchange on the aluminium sheet relative with main pole, is purpose with the carbon electrode that carries out uniform graining and dissolving main pole, as shown in Figure 4, impressed current anode is set preferably, makes the part shunting of alternating current.Among Fig. 4,11 is aluminium sheet, and 12 are drum-type roll (radial drum roller) radially, 13a and 13b are main poles, the 14th, electrolytic treatments liquid, the 15th, electrolyte supply mouth, the 16th, slit, the 17th, electrolyte passage, the 18th, impressed current anode, 19a and 19b are IGCTs, the 20th, AC power, the 40th, main electrolytic cell, the 50th, impressed current anode groove.By rectifier cell or switch element, make the part of current value become DC current and be diverted in the impressed current anode that is arranged on the groove different, the ratio of current value in the time of can controlling the aluminium sheet relative thus and be anode and the current value when being negative electrode with main pole with 2 main electrodes.Current ratio (ratio of electric weight summation when aluminium sheet is anode and the electric weight summation when being negative electrode) is preferred 0.9～3, and more preferably 0.9～1.0.

Electrolytic cell can use the known surface-treated electrolytic cells that are used for such as longitudinal type, platypelloid type, radial mode, and is preferred especially but the spy opens the radial mode electrolytic cell described in flat 5-No. 195300 communiques.Can be in the same way by the electrolyte in the electrolytic cell with respect to the direct of travel of reel aluminium sheet, also can be reverse.

Electrolytic cell can be separated into a plurality of.Electrolytic cell is separated into when a plurality of, and the electrolytic condition of each electrolytic cell can be identical, also can be different.

The processing of electrochemistry asperities is preferably carried out mangle with niproll after finishing, and then after carrying out the washing processing in 1～10 second again, carries out mangle with niproll.

Washing is handled the preferred playpipe that uses and is washed.Handle employed playpipe as washing, can use for example has a plurality of injection waters to diffuse into the playpipe of fan-shaped injection sheet on the width of aluminium sheet.Spray the preferred 20～100mm in interval of sheet, in addition, per 1 preferred 1～20L/min of liquid measure that sprays sheet.Playpipe preferably uses many.

＜the 2 corrosion treatment 〉

After the processing of electrochemistry asperities, preferably carry out the 2nd corrosion treatment.The purpose of carrying out the 2nd corrosion treatment is to make the dirt dissolving that is generated in the processing of electrochemistry asperities, and makes the marginal portion dissolving by the formed pit of electrochemistry asperities processing.Thus, the marginal portion of the formed pit of surperficial reason electrochemistry asperities processing is dissolved and is become smooth, owing to printing ink is difficult to hang on the marginal portion, so can obtain the outstanding original edition of lithographic printing plate of stain resistance.

The 2nd corrosion treatment is identical with the 1st corrosion treatment basically, but preferred 0.1～10 quality % of the aluminium ion concentration that contains in the aqueous slkali.The aluminum ions concentration that preferred especially use contains 4～8 quality % is the aqueous slkali of 20～40 quality %, and the aluminum ions concentration that perhaps contains 0.3～0.7 quality % is the aqueous slkali of 4～6 quality %.In addition, the liquid temperature is more preferably 30～80 ℃.

In addition, the preferred 0.01g/m of etching extent ²More than, more preferably 0.05g/m ²More than, further preferred 0.1g/m ²More than, in addition, preferred 10g/m ²Below, more preferably 3g/m ²Below, further preferred 0.3g/m ²Below.

＜the 2 abatement processes 〉

After carrying out the 2nd corrosion treatment,, preferably carry out pickling (the 2nd abatement processes) for the pollution (dirt) of removing remained on surface.The 2nd abatement processes fundamental sum first abatement processes is identical.

In the 2nd abatement processes, as abatement processes liquid, when use with the anodized of then carrying out in during the liquid of the electrolyte identical type used, can after abatement processes, omit mangle and washing processing by niproll.

In addition, the 2nd abatement processes is preferably carried out in the electrolytic cell anodized device that is used for anodized described later, carry out the cathode reaction processing on aluminium sheet.If like this, then owing to the independently abatement processes groove that there is no need to be provided for the 2nd abatement processes, so can reduce equipment cost.

＜anodized 〉

To aluminium sheet through above-mentioned processing, the also preferred anodized of implementing.Anodized can be carried out with the employed in the past method in this field.At this moment, for example, be 50～300g/L at sulfuric acid concentration, aluminum concentration is in the following solution of 5 quality %, is anodal closure with the aluminium sheet, can form anodic oxidation coating.As employed solution in anodized, can be separately or make up more than 2 kinds and use: sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, amide groups sulfonic acid etc. with following solution.

At this moment, can contain the common composition that contains in aluminium sheet, electrode, running water, the underground water etc. at least in the electrolyte.Have again, can also add the 2nd, the 3rd composition.Here said the 2nd, the 3rd composition can be enumerated for example ion of metals such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn; Cations such as ammonium ion; Anion such as nitrate ion, carbonic acid ion, chloride ion, phosphate ion, fluoride ion, sulfurous acid ion, metatitanic acid ion, silicic acid ion, borate ion also can contain the concentration about 0～10000ppm.

The condition of anodized is carried out various variations according to the difference of the electrolyte that uses, thus can not decide without exception, but concentration of electrolyte is 1～80 quality % usually, and the liquid temperature is 5～70 ℃, and current density is 0.5～60A/dm ², voltage is 1～100V, electrolysis time is that 15 seconds～50 minutes condition is more suitable, can be adjusted into desired anodic oxidation coating amount.

In addition, can also use the method described in following each communique: the spy opens clear 54-No. 81133, the spy opens clear 57-No. 47894, the spy opens clear 57-No. 51289, the spy opens clear 57-No. 51290, the spy opens clear 57-No. 54300, the spy opens clear 57-No. 136596, the spy opens clear 58-No. 107498, the spy opens clear 60-No. 200256, the spy opens clear 62-No. 136596, the spy opens clear 63-No. 176494, No. 4-176897, Te Kaiping, No. 4-280997, Te Kaiping, No. 6-207299, Te Kaiping, No. 5-24377, Te Kaiping, No. 5-32083, Te Kaiping, No. 5-125597, Te Kaiping, No. 5-195291, Te Kaiping.

Wherein, open clear 54-No. 12853 and spy as the spy and open described in clear 48-No. 45303 communiques, preferably use sulfuric acid solution as electrolyte.Preferred 10～the 300g/L of sulfuric acid concentration in the electrolyte (1～30 quality %), more preferably 50～200g/L (5～20 quality %), in addition, the preferred 1～25g/L of aluminium ion concentration (0.1～2.5 quality %), more preferably 2～10g/L (0.2～1 quality %).Aforesaid electrolyte for example can be by being to add aluminum sulfate in the dilute sulfuric acid of 50～200g/L to wait and modulate at sulfuric acid concentration.

The management of the composition of electrolyte is preferred to be used and same method during above-mentioned nitric acid electrolysis etc., and according to, electrical conductivity corresponding with the matrix of sulfuric acid concentration and aluminium ion concentration and proportion and temperature, or electrical conductivity and ultrasonic propagation velocity and temperature are managed.

Preferred 25～55 ℃ of the liquid temperature of electrolyte, more preferably 30～50 ℃.

When in containing the electrolyte of sulfuric acid, carrying out anodized, direct current can be applied between aluminium sheet and the polarity, also interchange can be applied.

When aluminium sheet is applied direct current, the preferred 1～60A/dm of current density ², more preferably 5～40A/dm ²

When carrying out anodized continuously, concentrate on the part of aluminium sheet for fear of electric current, promptly so-called " burning " (tunicle than around part of thickening) phenomenon is preferably when beginning anodized at first, with 5～10A/dm ²Low current density apply electric current, along with the carrying out of anodized, make current density be increased to 30～50A/dm ²Or more than it.

Particularly, the electric current of dc source distributes, and the electric current that preferably makes the dc source of downstream side is more than the electric current of dc source of upstream side.Distribute by carrying out aforesaid electric current, be not easy to take place the so-called phenomenon of burning, consequently Gao Su anodized becomes possibility.

When carrying out anodized continuously, the preferred employing by electrolyte carried out the solution power supply mode of aluminium sheet power supply.

By under such condition, carrying out anodized, can obtain having the perforated membrane in a large amount of holes that is known as pore (micropore), usually, its average pore size is about 5～50nm, and average hole density is about 300～800/μ m ²

Preferred 1～the 5g/m of the amount of anodic oxidation coating ²If be 1g/m ²More than, be difficult in spite of wound on the version.If be 5g/m ²Below, do not need a large amount of electric power in the manufacturing, economically feasible.The amount of anodic oxidation coating is 1.5～4g/m more preferably ²Near the difference of the anodic oxidation coating amount between in addition, the central portion of aluminium sheet and the edge part is with 1g/m ²Below be advisable.

In addition, be implemented the preferred 0.1～1g/m of amount of anodic oxidation coating at the back side of the face of electrochemistry asperities processing ²If be 0.1g/m ²More than, the back side is difficult in spite of wound, and as original edition of lithographic printing plate, when stack, the image recording layer that contacts with the back side is difficult in spite of wound.If be 1g/m ²Below, then economically feasible.

As the employed electrolysis unit of anodized, can use the spy to open clear 48-No. 26638, spy and open clear 47-No. 18739, special public clear 58-No. 24517, spy and open the device described in each communique etc. of 2001-No. 11698.

Wherein, device shown in Figure 5 is more suitable.Fig. 5 is the device of anodized is carried out in expression to the surface of aluminium sheet a routine skeleton diagram.

In anodized device 410 shown in Figure 5, for by electrolyte to aluminium sheet 416 energising, at the upstream side of the direct of travel of aluminium sheet 416 power supply groove 412 is set, at downstream side anodized groove 414 is set.Aluminium sheet 416 is transported according to the direction shown in the arrow among Fig. 5 by deflector roll (pass roller) 422 and 428.In the power supply groove 412 that aluminium sheet 416 is imported at first, be provided with the anode 420 that is connected with the positive pole of dc source 434, aluminium sheet 416 becomes negative electrode.Therefore, in aluminium sheet 416 cathode reaction takes place.

In the anodized groove 414 that next aluminium sheet 416 is imported into, be provided with the negative electrode 430 that is connected with the negative pole of dc source 434, aluminium sheet 416 becomes anode.Therefore, in the aluminium sheet 416 anode reaction takes place, the surface of aluminium sheet 416 forms anodic oxidation coating.

Preferred 50～the 200mm in the interval of aluminium sheet 416 and negative electrode 430.Negative electrode 430 uses aluminium.Escape from system easily for the hydrogen that anode reaction is produced, negative electrode 430 is not the electrode with wide area preferably, but is divided into a plurality of electrodes along the direct of travel of aluminium sheet 416.

Between power supply groove 412 and anodized groove 414, as shown in Figure 5, the preferred groove that does not accumulate electrolyte that is known as medial launder 413 that is provided with.By medial launder 413 is set, can suppress electric current without aluminium sheet 416, and by-passing is from anode 420 to negative electrode 430.Niproll 424 preferably is set to carry out mangle in medial launder 413, by-pass current is reduced to seldom.Electrolyte by mangle flows out is discharged to outside the anodized device 410 from leakage fluid dram 442.

In order to reduce the loss of voltage, electrolyte 426 temperature that the electrolyte 418 that stays of storage in the power supply groove 412 is stayed than storage in the anodized groove 414 are higher and/or concentration is higher.In addition, electrolyte 418 and 426 composition, temperature etc. are by the decisions such as cost of the hardness of the shape of the micropore that forms efficient, anodic oxidation coating of anodic oxidation coating, anodic oxidation coating, voltage, electrolyte.

In power supply groove 412 and the anodized groove 414, carry out feed flow from feed flow nozzle 436 and 438 ejection electrolyte.Certain for the distribution that makes electrolyte, prevent that the local current of the aluminium sheet 416 in the anodized groove 414 from concentrating, feed flow nozzle 436 and 438 is provided with slit, and the liquid with the ejection of making flows structure stable on width.

In anodized groove 414, from anode 430, shield 440 is set at the opposition side of clamping aluminium sheet 416, suppress the opposite side of one side of wanting to form anodic oxidation coating that electric current flows to aluminium sheet 416.Preferred 5～the 30mm in the interval of aluminium sheet 416 and shield 440.Dc source 434 preferred uses are a plurality of, connect side of the positive electrode jointly and use.Thus, can control CURRENT DISTRIBUTION in the anodized groove 414.

Also have, when carrying out anodized, also can use 1 anodized device 410, still preferred direct of travel at aluminium sheet is arranged 2～5 anodized devices 410 side by side and is handled continuously.Handle continuously if arrange 2～5 anodized devices 410 side by side, then can carry out high speed processing effectively and cut down electrification at the direct of travel of aluminium sheet, thereby effectively.

＜sealing of hole is handled 〉

Among the present invention, can also be as required, the sealing of hole that is sealed in the micropore that exists in the anodic oxidation coating is handled.Handle by carrying out sealing of hole, can improve the development (sensitivity) of original edition of lithographic printing plate.

As everyone knows, anodic oxidation coating be with the direction of tunicle surface approximate vertical on have the multiple aperture plasma membrane of the pore that is called micropore.Among the present invention, preferably in anodized, carry out the sealing of hole of high sealing of hole rate and handle.The sealing of hole rate is preferred more than 50%, and is more preferably more than 70%, further preferred more than 90%.Wherein, " sealing of hole rate " defines with following formula.

Surface area * 100% before sealing of hole rate=(surface area behind the surface area-sealing of hole before the sealing of hole)/sealing of hole

Surface area can use the surface area measurement mechanism (for example, QUANTASORB (カ Application ソ-Block), the shallow ア イ of soup オ ニ Network ス corporate system) of for example simple and easy BET mode to measure.

Processing has no particular limits to sealing of hole, can use known method in the past.Can enumerate for example hot water treatment, boiling water treating, steam treatment, bichromate is handled, nitrite treatments, ammonium acetate is handled, the electro-deposition sealing of hole is handled, as open the zirconium fluoride acid treatment of record in clear 36-No. 22063 communiques etc. the spy, the usefulness of putting down in writing in 9-No. 244227 communiques of Te Kaiping contains the processing of the aqueous solution of phosphate and inorganic fluoride, the usefulness of putting down in writing in 9-No. 134002 communiques of Te Kaiping contains the processing of sugar aqueous solution, the spy opens the processing of putting down in writing in 2000-No. 81704 communiques and 2000-No. 89466 communiques of Te Kai with the aqueous solution of titaniferous and fluorine, United States Patent (USP) 3, the alkali silicate of record is handled in 181, No. 461 specifications etc.

As the example that the sealing of hole that is fit to is handled, can enumerate alkali silicate and handle.The alkali silicate processing can be 10～13 alkali metal silicate aqueous solution at 25 ℃ that do not cause the dissolving of solution gelization and the anodic oxidation coating following pH of use, suitably selects treatment conditions such as alkali metal silicate salinity, treatment temperature, processing time to carry out.As the alkali silicate that is fit to, can enumerate for example sodium metasilicate, potassium silicate, lithium metasilicate.In addition, in order to adjust the pH of alkali metal silicate aqueous solution than the highland, can mix NaOH, potassium hydroxide, lithium hydroxide etc.

In addition, also mixed alkaline earth slaine and/or 4 families (IVA family) slaine in alkali metal silicate aqueous solution as required.As this alkali salt, can enumerate for example nitrate such as calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate; Water soluble salts such as the sulfate of alkaline-earth metal, hydrochloride, phosphate, acetate, oxalates, borate.As 4 families (IVA family) slaine, can enumerate for example titanium tetrachloride, titanium trichloride, titanium potassium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetra iodide, basic zirconium chloride, zirconium dioxide, zirconium chloride etc.Alkali salt and 4 families (IVA family) slaine can separately or make up more than two kinds and use.

Preferred 0.01～10 quality % of the concentration of alkali metal silicate aqueous solution, more preferably 0.05～5.0 quality %.

As the example that the sealing of hole that is fit to is handled, can enumerate the zirconium fluoride acid treatment.The zirconium fluoride acid treatment can be used and fluoridize sodium zirconate, fluoridizes zirconium fluoride hydrochlorates such as potassium zirconium and carry out.Wherein, the preferred use fluoridized sodium zirconate.Thus, the development of original edition of lithographic printing plate (sensitivity) is outstanding.Preferred 0.01～2 quality % of concentration that is used for the acid-treated zirconium fluoride acid solution of zirconium fluoride, more preferably 0.1～0.3 quality %.

The zirconium fluoride acid salt solution preferably contains sodium dihydrogen phosphate.Preferred 0.01～3 quality % of the concentration of sodium dihydrogen phosphate, more preferably 0.1～0.3 quality %.

The zirconium fluoride acid salt solution also can contain aluminium ion.At this moment, the preferred 1～500mg/L of the aluminium ion concentration of zirconium fluoride acid salt solution.

Preferred 20～90 ℃ of the temperature that sealing of hole is handled, more preferably 50～80 ℃.

Preferred 1～20 second of the time (dip time in solution) that sealing of hole is handled, more preferably 5～15 seconds.

In addition; can be as required after carrying out the sealing of hole processing; can carry out above-mentioned alkali silicate processing, surface treatments such as processing as described below; wherein; back one handle be impregnated in contain polyvinylphosphonic acid, polyacrylic acid, side chain have sulfo group polymer or copolymer, have the solution of organic compound that the spy opens amino of putting down in writing in flat 11-No. 231509 communiques and the group that is selected from phosphono (ホ ス Off ィ Application base), phosphino-(ホ ス ホ Application base) and phosphate or its salt etc., the processing that perhaps is coated with etc.

After sealing of hole is handled, preferably carry out hydrophilicity-imparting treatment described later.

＜hydrophilicity-imparting treatment 〉

After the anodized or after the sealing of hole processing, also can carry out hydrophilicity-imparting treatment.As hydrophilicity-imparting treatment, can enumerate for example United States Patent (USP) the 2nd, 946, the potassium zirconium of fluoridizing described in No. 638 specifications is handled, United States Patent (USP) the 3rd, 201, phosphomolybdate described in No. 247 specifications is handled, BP the 1st, 108, alkyl titanate described in No. 559 is handled, Deutsche Bundespatent the 1st, 091, No. 433 the described polyacrylic acid of specification is handled, Deutsche Bundespatent the 1st, 134, No. 093 specification and BP the 1st, 230, No. 447 the described polyvinylphosphonic acid of specification is handled, the described phosphonic acids of special public clear 44-No. 6409 communiques is handled, United States Patent (USP) the 3rd, 307, No. 951 the described phytic acid of specification is handled, the spy opens the processing of the salt of clear 58-No. 16893 communiques and described lipophile organic high molecular compound of clear 58-No. 18291 communiques of Te Kai and the formation of divalent metal, as United States Patent (USP) the 3rd, 860, No. 426 described settings of specification contain water-soluble metal salt (as, the processing of the priming coat of hydrophilic cellulose zinc acetate) (as, carboxymethyl cellulose), the spy opens the processing that the described water-soluble polymer that will have sulfo group of clear 59-No. 101651 communiques carries out primary coat.

In addition, can also enumerate the processing of carrying out primary coat with following material etc., promptly the spy opens the described phosphate of clear 62-No. 019494 communique, the spy opens the described soluble epoxide compound of clear 62-No. 033692 communique, the spy opens the described phosphoric acid modification starch of clear 62-No. 097892 communique, the spy opens the diamine compound described in clear 63-No. 056498 communique, the spy opens the described amino acid whose inorganic or organic salt of clear 63-No. 130391 communiques, the spy opens the described organic phospho acid that contains carboxyl or hydroxyl of clear 63-No. 145092 communiques, the spy opens the described compound that contains amino and phosphonate group of clear 63-No. 165183 communiques, the described specific carboxylic acid derivates of 2-No. 316290 communiques of Te Kaiping, the described phosphate of 3-No. 215095 communiques of Te Kaiping, the described compound that has the oxyacid base of 1 amino and 1 phosphorus of 3-No. 261592 communiques of Te Kaiping, Te Kaiping 5-No. 246171 aliphatic or aromatic series phosphonic acids such as the described phenyl-phosphonic acid of communique, the described compound that contains the S atom as thiosalicylic acid of 1-No. 307745 communiques of Te Kaiping, 4-No. 282637 communiques of Te Kaiping are described to have the compound etc. of group of the oxyacid of phosphorus.

Have again, can also open the described acid dyes of clear 60-No. 64352 communiques with the spy and carry out painted.

In addition, the method for preferably carrying out hydrophilicity-imparting treatment is: the method for flooding in the aqueous solution of alkali silicates such as sodium metasilicate, potassium silicate; Coating hydrophilic vinyl polymer or hydrophilic compounds form the method for hydrophilic priming coat etc.

With the hydrophilicity-imparting treatment that the aqueous solution of alkali silicates such as sodium metasilicate, potassium silicate carries out, can be according to United States Patent (USP) the 2nd, 714, method and step described in No. 066 specification and the 3rd, 181, No. 461 specifications of United States Patent (USP) are implemented.

As alkali silicate, can enumerate for example sodium metasilicate, potassium silicate, lithium metasilicate etc.The aqueous solution of alkali silicate also can contain NaOH, potassium hydroxide, lithium hydroxide etc. in appropriate amount ground.

In addition, the aqueous solution of alkali silicate can also contain alkali salt or 4 families (IVA family) slaine.Alkali salt can be enumerated for example nitrate of calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate etc.; Sulfate; Hydrochloride; Phosphate; Acetate; Oxalates; Borate etc.4 families (IVA family) slaine can be enumerated for example titanium tetrachloride, titanium trichloride, titanium potassium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetra iodide, basic zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium chloride.These alkali salts and 4 families (IVA family) slaine can use more than 2 kinds alone or in combination.

Handling the Si amount of adsorbing by alkali silicate can measure with fluorescent x-ray analysis device, and its adsorbance preferably is about 1.0～15.0mg/m ²

Handle by this alkali silicate, can obtain the effect of the surface of support body for lithographic plate printing plate with respect to the dissolubility resistent raising of alkaline-based developer, can suppress the wash-out of aluminium component in developer solution, reduce generation by the tired caused development gas of developer solution.

Have again,, can open condition and the step described in clear 59-No. 101651 communiques and clear 60-No. 149491 communiques of Te Kai according to the spy and implement by the hydrophilicity-imparting treatment that the formation of hydrophilic priming coat is carried out.

As the hydrophilic vinyl polymer that this method is used, the p styrene sulfonic acid etc. that can enumerate polyvinyl sulfonic acid for example, contains sulfo group contains the copolymer of common vinyl polymerized compound such as the vinyl polymerized compound of sulfo group and (methyl) alkyl acrylate.In addition, the hydrophilic compounds that this method is used can enumerate for example to contain being selected from-NH ₂Base ,-compound of at least a group in COOH base and the sulfo group.

＜drying 〉

After obtaining support body for lithographic plate printing plate as mentioned above, before image recording layer is set, preferably drying is carried out on the surface of support body for lithographic plate printing plate.Drying preferably surface-treated is last handle after, washing is handled and carry out carrying out after the mangle with niproll again.

Baking temperature is preferred more than 70 ℃, and is more preferably more than 80 ℃, preferred below 110 ℃ in addition, more preferably below 100 ℃.

Drying time is preferred more than 1 second, and is more preferably more than 2 seconds, preferred in addition below 20 seconds, more preferably below 15 seconds.

[original edition of lithographic printing plate]

On the support body for lithographic plate printing plate that obtains by the present invention, image recording layer can be set obtain original edition of lithographic printing plate of the present invention.Use photosensitive composite in the image recording layer.

As being applicable to photosensitive composite of the present invention, can enumerate the thermal positive type photosensitive composition that for example contains alkali solubility macromolecular compound and photo-thermal conversion material (below, said composition and its image recording layer of use are called " thermal positive type "), the hot negative photosensitive composition (following be called equally " hot minus ") that contains curing property compound and photo-thermal conversion material, photo-polymerization type photosensitive composite (following be called equally " photopolymer type "), the negative photosensitive composition (following be called equally " common minus ") that contains diazo resin or optical cross-linked resin, the positive light sensitivity composition (following be called equally " common eurymeric ") that contains quinone diazido compound, the photosensitive composite (following be called equally " non-processor type ") that does not need special developing procedure, preferred especially thermal positive type, hot minus, the non-processor type.Below these photosensitive composites that are fit to are illustrated.

＜thermal positive type 〉

＜photosensitive layer 〉

The photosensitive composite of thermal positive type contains alkali solubility macromolecular compound and photo-thermal conversion material.In the image recording layer of thermal positive type, photo-thermal conversion material is transformed into heat with luminous energy such as infrared lasers, and this heat energy is effectively removed the interaction of the alkali decreased solubility that makes the alkali solubility macromolecular compound.

As the alkali solubility macromolecular compound, can enumerate the resin and the mixture more than 2 kinds thereof that contain acidic groups in the molecule for example.Particularly contain phenol hydroxyl, sulfoamido (-SO ₂NH-R (in the formula, the R representation hydrocarbyl)), active imino group (-SO ₂NHCOR ,-SO ₂NHSO ₂R ,-CONHSO ₂R (in various, R is the meaning same as described above)) etc. the resin of acidic groups is considered more satisfactory from the dissolubility aspect to alkaline developer.

Especially the outstanding viewpoint of image forming in by the exposure of light such as infrared laser, the resin that preferably contains the phenol hydroxyl, can suitably enumerate phenol-formaldehyde resin for example, metacresol-formaldehyde resin, paracresol-formaldehyde resin ,/to cresols-formaldehyde resin, phenol/cresols (between can being, to and/to mixing any) mixing-formaldehyde resin novolac resins such as (phenol-cresols-formaldehyde cocondensation resin).

In addition, also can suitably be set forth in macromolecular compound that the spy opens record in 2001-No. 305722 communiques (particularly [0023]～[0042]), the macromolecular compound of in the spy opens 2001-No. 215693 communiques, putting down in writing that contains the represented repetitive of useful general formula (1), open the macromolecular compound of putting down in writing in 2002-No. 311570 communiques (particularly [0107]) the spy.

As photo-thermal conversion material, consider that from the recording sensitivity aspect region of ultra-red that can suitably be set forth in wavelength 700～1200nm has the pigment or the dyestuff of photo-absorption region.As dyestuff, for example can enumerate azo dyes, metallic complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dye, benzoquinone imine dyestuff, methine dyes, anthocyanin dye, Si Kualin (ス Network ワ リ リ ウ system) pigment, pyralium salt, metal mercaptide salt complex (as, mercaptan nickel coordination compound).Wherein, preferred anthocyanin dye, especially preferred spy opens the represented anthocyanin dye of putting down in writing in 2001-No. 305722 communiques of general formula (1).

In the photosensitive composite of thermal positive type, can contain the dissolving inhibitor.As the dissolving inhibitor, can suitably enumerate the middle dissolving inhibitor of putting down in writing in [0053]～[0055] that Ru Te opens 2001-No. 305722 communiques.

In addition, in the photosensitive composite of thermal positive type, as additive, preferably contain the sensitivity conditioning agent, obtain the oven dry agent of visual image after the heating that is used to expose immediately, as the compounds such as dyestuff of image colouring agent, be used to surfactant that coating and Treatment Stability are improved.For these compounds, preferably as the spy open the compound of putting down in writing in [0056]～[0060] of 2001-No. 305722 communiques.

Except above-mentioned, the preferred photosensitive composite of opening write up in 2001-No. 305722 communiques the spy that uses.

In addition, the image recording layer of thermal positive type is not limited to individual layer, also can be 2 layers of structure.

Image recording layer (image recording layer of multilayer system) as 2 layers of structure, can suitably enumerate following type: in a side the outstanding bottom of anti-brush and solvent resistance (below be called " A layer ") is set, the eurymeric image is set above it forms the good layer of property (below be called " B layer ") near support.The type is highly sensitive, can realize wide development tolerance.The B layer generally contains photo-thermal conversion material.Photo-thermal conversion material can be listed as the aforesaid dyestuff of suitable act.

As employed resin in the A layer, consider that from anti-brush and the good aspect of solvent resistance the monomer that can suitably enumerate to contain sulfoamido, active imino group, phenol hydroxyl etc. is the polymer of copolymer composition.As employed resin in the B layer, can suitably enumerate the aqueous alkaline solution-soluble resin that contains the phenol hydroxyl.

In A layer and the employed composition of B layer, except described resin, can also contain various additives as required.Particularly, it is more suitable that the spy opens the various additives of putting down in writing in 2002-No. 3233769 communiques [0062]～[0085].In addition, the above-mentioned spy additive of opening record in [0053]～[0060] of 2001-No. 305722 communiques also can be suitable for.

For each composition and the content thereof that constitute A layer and B layer, preferred spy opens the related content of putting down in writing in flat 11-No. 218914 communiques.

＜intermediate layer 〉

The intermediate layer preferably is set between the image recording layer of thermal positive type and the support.As the composition that the intermediate layer is contained, can suitably enumerate the various organic compounds that the spy opens [0068] middle record of 2001-No. 305722 communiques.

＜other 〉

For the manufacture method and the method for platemaking of the image recording layer of thermal positive type, can use the spy to open the method for write up in 2001-No. 305722 communiques.

＜hot minus 〉

The photosensitive composite of hot minus contains curing property compound and photo-thermal conversion material.The image recording layer of hot minus is solidified to form the photosensitive layer of the minus of image portion by light-struck parts such as infrared lasers.

＜overlapping layer 〉

As one type of the image recording layer of hot minus, can suitably enumerate the image recording layer (overlapping layer) of overlapping type.Overlapping layer contains the free-radical polymerised compound and the adhesive polymer of photo-thermal conversion material, free radical generating agent, conduct curing property compound.In overlapping layer, photo-thermal conversion material is transformed into heat with the infrared ray that absorbs, and free radical generating agent is produced free radical by this thermal decomposition, the free radical chain ground polymerization of free-radical polymerised compound because of producing, and solidify.

As photo-thermal conversion material, can be exemplified as employed photo-thermal conversion material in above-mentioned thermal positive type.As the concrete example of particularly preferred anthocyanin pigment, can enumerate the material in [0017]～[0019] that is documented in the spy and opens 2001-No. 133969 communiques.

As free radical generating agent, can suitably enumerate salt.Particularly preferred salt is documented in [0030]～[0033] that the spy opens 2001-No. 133969 communiques.

As free-radical polymerised compound, can enumerate have at least 1, the compound of the terminal ethene unsaturated bond more than 2 preferably.

As adhesive polymer, can suitably enumerate the wire organic polymer.Can suitably enumerate the wire organic polymer that water or weak base glassware for drinking water is had solubility or swellability.Wherein, have (methyl) acrylic resin of unsaturated group such as pi-allyl, acryloyl group or benzyl, carboxyl at side chain, it is more suitable to consider from the balanced good aspect of film-strength, sensitivity and development.

About free-radical polymerised compound and adhesive polymer, can use the spy to open the material of the middle write up in [0036]～[0060] of 2001-No. 133969 communiques.

In the photosensitive composite of hot minus, preferably contain the middle additive of putting down in writing (for example, being used to improve the surfactant of coating) in [0061]～[0068] that the spy opens 2001-No. 133969 communiques.

For the manufacture method and the method for platemaking of overlapping layer, can use the spy to open the method for write up in 2001-No. 133969 communiques.

＜sour cross-linked layer 〉

In addition, as one type of the image recording layer of hot minus, can also suitably enumerate the image recording layer (sour cross-linked layer) of sour cross-linking type.The acid cross-linked layer contains photo-thermal conversion material, hot acid agent, as the alkali solubility macromolecular compound that pass through sour crosslinked compound (crosslinking agent) and in the presence of acid, can react with crosslinking agent that solidifies the property compound.In the acid cross-linked layer, photo-thermal conversion material is transformed into heat with the infrared ray that absorbs, and hot acid agent is produced acid by this thermal decomposition, and crosslinking agent and alkali solubility macromolecular compound react by the acid that produces, and solidifies.

As photo-thermal conversion material, can enumerate with overlapping layer in employed same material.

As hot acid agent, can be exemplified as heat-decomposing compound such as employed acid agent in the phototropic agent of photopolymerisable light trigger, pigment, the little resist (マ イ Network ロ レ ジ ス ト) etc.

As crosslinking agent, can enumerate the aromatic compound that replaces as by methylol or alkoxy methyl; Compound with N-methylol, N-alkoxy methyl or N-acyloxy methyl; Epoxide.

As the alkali solubility macromolecular compound, can enumerate the polymer that contains hydroxyaryl as novolac resin, side chain.

＜photopolymer type 〉

Photopolymer type photosensitive composite contains addition polymerization compound, Photoepolymerizationinitiater initiater and polymer binder.

As the addition polymerization compound, can suitably enumerate the compound that contains ethene unsaturated bond that can addition polymerization.The compound that contains the ethene unsaturated bond is the compound that has the ethene unsaturated bond on the end.Particularly, monomer, prepolymer, their chemical forms such as mixture are for example arranged.As the example of monomer, can enumerate unsaturated carboxylic acid (as, acrylic acid, methacrylate, itaconic acid, maleic acid) and the acid amides that forms of aliphatic polyol the compound ester, unsaturated carboxylic acid and the aliphatic polyamine compound that form.

In addition, as the addition polymerization compound, can also suitably enumerate carbamate is the addition polymerization compound.

As Photoepolymerizationinitiater initiater, can select to use the paralled system (light initiation system) of various Photoepolymerizationinitiater initiaters or the Photoepolymerizationinitiater initiater more than 2 kinds aptly according to the wavelength of the light source that uses.For example can suitably enumerating, the spy opens the initiator system of putting down in writing in [0021]～[0023] of 2001-No. 22079 communiques.

Polymer binder not only works as the tunicle formation agent of photo-polymerization type photosensitive composite, and image recording layer is dissolved in the alkaline developer, therefore uses the organic high molecular polymer that alkaline water is had solubility or swellability.As aforesaid organic high molecular polymer, can suitably enumerate the spy and open the material of putting down in writing in [0036]～[0063] of 2001-No. 22079 communiques.

In the photo-polymerization type photosensitive composite of photopolymer type, preferably contain record in [0079]～[0088] that the spy opens 2001-No. 22079 communiques additive (as, be used to improve surfactant, colouring agent, plasticizer, the thermal polymerization inhibitor of coating).

In addition, on the image recording layer of photopolymer type, the polymerization inhibitory action for anti-block preferably is provided with oxygen barrier property protective layer.As the polymer that contains in the oxygen barrier property protective layer, can be exemplified as polyvinyl alcohol, its copolymer.

Intermediate layer or the adhesive linkage of also preferred setting as the middle record in [0124]～[0165] that the spy opens 2001-No. 228608 communiques arranged again.

＜common minus 〉

The photosensitive composite of common minus contains diazo resin or optical cross-linked resin.Wherein, can suitably enumerate the photosensitive composite of the macromolecular compound (adhesive) that contains diazo resin and alkali solubility or swellability.

As diazo resin, can enumerate the condensation product that compound that for example aromatic series diazol and formaldehyde etc. contains active carbonyl group forms; As organic solvent solubility diazo resin inorganic salts to the product of the condensation product of benzene diazonium amine and formaldehyde and hexafluorophosphate or tetrafluoroborate.Particularly preferably in the spy open put down in writing in clear 59-No. 78340 communiques contain the above HMW diazonium compound of 20 moles of above hexamers of %.

As adhesive, can be exemplified as and contain acrylic acid, methacrylic acid, crotonic acid or maleic acid copolymer as necessary composition.Specifically, can enumerate and open the multiple copolymer that monomers such as (methyl) acrylic acid 2-hydroxyl ethyl ester putting down in writing in clear 50-No. 118802 communiques, (methyl) acrylonitrile, (methyl) acrylic acid form as the spy, open alkyl acrylate, (methyl) acrylonitrile and the formed multiple copolymer of unsaturated carboxylic acid putting down in writing in clear 56-No. 4144 communiques as the spy.

In the photosensitive composite of common minus, as additive, preferably contain the surfactant of opening compounds such as the oven dry agent put down in writing in [0014]～[0015] of flat 7-No. 281425 communiques, dyestuff, the plasticizer that is used to give soft film coating and abrasion performance, development accelerant the spy, being used to improve coating.

Below the photosensitive layer of common minus, preferably be arranged on the spy and open the intermediate layer of putting down in writing in 2000-No. 105462 communiques of containing macromolecular compound, this macromolecular compound has the constituent that contains acid group and contains the constituent of base.

＜common eurymeric 〉

The photosensitive composite of common eurymeric contains quinone diazido compound.Wherein, can also suitably enumerate the photosensitive composite that contains o-quinone diazido compound and alkali solubility macromolecular compound.

As o-quinone diazido compound, for example can enumerate 1, ester, United States Patent (USP) the 3rd that 2-naphthoquinones-2-diazido-5-sulfonic acid chloride and phenol-formaldehyde resin or cresols-formaldehyde resin forms, 635, the ester that 1, the 2-naphthoquinones-2-diazido-5-sulfonic acid chloride put down in writing in No. 709 specifications and 1,2,3,-thrihydroxy-benzene-acetone resin forms.

As the alkali solubility macromolecular compound, can enumerate for example phenol-formaldehyde resin, cresols-formaldehyde resin, phenol-cresols-formaldehyde cocondensation resin, polycarboxylated styrene, N-(4-hydroxy phenyl) Methacrylamide copolymer, to open the polymer that contains carboxyl put down in writing in flat 7-No. 36184 communiques, open the acrylic resin that contains the phenol hydroxyl put down in writing in clear 51-No. 34711 communiques, open the acrylic resin that contains sulfoamido, the carbamate put down in writing in flat 2-No. 866 communiques the spy the spy the spy be resin.

In the photosensitive composite of common eurymeric, as additive, preferably contain the spy and open the compound such as sensitivity conditioning agent, oven dry agent, dyestuff of record in [0024]～[0027] of flat 7-No. 92660 communiques or open the surfactant of putting down in writing in [0031] of flat 7-No. 92660 communiques that is used to improve coating the spy.

Below the photosensitive layer of common eurymeric, the preferred setting and the same intermediate layer, intermediate layer that is applicable to above-mentioned common minus.

＜non-processor type 〉

As the photosensitive composite of non-processor type, can enumerate thermoplasticity microparticle polymer type, microcapsule-type, contain sulfonic acid generation polymer-type.They all are the thermosensitive types that contains photo-thermal conversion material.Employed same dyestuff in choosing of fine quality of photo-thermal transformed object and the above-mentioned thermal positive type.

The photosensitive composite of thermoplasticity microparticle polymer type is that the microparticle polymer of hydrophobicity and hot melt property is dispersed in the hydrophilic macromolecule matrix and forms.In the image recording layer of thermoplasticity microparticle polymer type, the heat fusion that hydrophobic microparticle polymer is produced because of exposure, fusion forms water repellent region, i.e. image portion mutually.

As microparticle polymer, the fusion that obtains by heat fusing between the particulate preferably, the surface is that the hydrophily and the material that might be distributed in the hydrophilic composition such as damping water are desirable more.Particularly, can suitably enumerate Research Disclosure No.33303 (in January, 1992), spy opens flat 9-No. 123387, spy and opens flat 9-No. 131850, spy and open each communique, european patent application that flat 9-No. 171249 and spy open flat 9-No. 171250 and disclose the thermoplasticity microparticle polymer of putting down in writing in the 931st, No. 647 specification etc.Wherein, also preferred polystyrene and polymethyl methacrylate.As the microparticle polymer on possess hydrophilic property surface, can be exemplified as polymer itself is hydrophilic material; Make hydrophilic compounds such as polyvinyl alcohol, polyethylene glycol be adsorbed on microparticle polymer surface and make the material of surface hydrophilic.

Microparticle polymer preferably contains reactive functional groups.

As the photosensitive composite of microcapsule-type, the microcapsule-type of bag in the compound that will have heat reactivity functional group of can suitably enumerate the material in the spy opens 2000-No. 118160 communiques, put down in writing, in the spy opens 2001-No. 277740 communiques, putting down in writing.

Produce the sulfonic acid generation polymer that uses in the photosensitive composite of polymer-type as containing sulfonic acid, can be exemplified as the spy and open the polymer that has sulfonate group, disulfonic acid base or the second month in a season or uncle's sulfoamido on the side chain of putting down in writing in flat 10-No. 282672 communiques.

By containing hydrophilic resin in the photosensitive composite that makes the non-processor type, not only development becomes well on machine, and the film-strength of photosensitive layer itself also improves.As hydrophilic resin, preference is as containing material, the hydrophilic collosol and gel transformation series binding resin of hydrophilic groups such as hydroxyl, carboxyl, ethoxy, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl.

The image recording layer of non-processor type does not need special developing procedure, can develop on printing machine.About the manufacture method and the Plate making printing method of the image recording layer of non-processor type, can use the spy to open the method for write up in 2002-No. 178655 communiques.

＜back coating 〉

As mentioned above, the back side of the original edition of lithographic printing plate of the present invention that on resulting support body for lithographic plate printing plate, various image recording layers is set and obtains by the present invention, the cover layer that is made of organic high molecular compound can be set as required, so that prevent the scratch of image recording layer when overlapping.

[method for platemaking (manufacture method of lithographic plate)]

Used original edition of lithographic printing plate,, become lithographic plate by being fit to the various processing methods of image recording layer by the resulting support body for lithographic plate printing plate of the present invention.

As the light source of the active ray that is used for image exposure, can enumerate for example mercury vapor lamp, metal halide lamp, xenon lamp, chemical lamp.As laser beam, can enumerate for example helium-Ne laser (He-Ne laser), argon laser, krypton laser, helium-cadmium laser, KrF excimer laser, semiconductor laser, YAG laser, YAG-SHG laser.

After described exposure, under image recording layer was any situation in thermal positive type, hot minus, common minus, common eurymeric and the photopolymer type, preferably developing with developer solution after exposure obtained lithographic plate.

The preferred alkaline-based developer of developer solution does not more preferably contain the alkaline aqueous solution of organic solvent in fact.

In addition, it is also more satisfactory not contain the developer solution of alkali silicate in fact.As the method for using the developer solution do not contain alkali silicate in fact to develop, can use the method for opening write up in flat 11-No. 109637 communiques the spy.

Have again, also can use the developer solution that contains alkali silicate.

Embodiment

Specify the present invention below by illustrated embodiment.But the present invention is not limited to these embodiment.

1. the aluminium sheet embossing finishing manufacturing of roller

Use is quenched tool steel (SKD11) and is formed the roller of Hv750, carries out following processing (1)～(5) successively, thereby obtains each aluminium sheet embossing finishing roller.

(1) mirror ultrafinish is handled

The surface finish milled processed is carried out in processing as mirror ultrafinish, removes the vestige of the grinding stone on mixing roll surface.On the surface after the grinding, mean roughness R _aBe 0.2 μ m, maximum height R _MaxBe 1 μ m.In addition, mean roughness R _aWith maximum height R _MaxRespectively according to the arithmetic average roughness R of JIS B0601-1994 _aWith maximum height R _MaxMeasurement measure.

(2) blasting treatment

By on the surface of roller, carry out the air-jet method of the alumina particle of twice use #80 sieve mesh (mesh) as the grid material, carry out the asperities processing.About each time air-jet method, expulsion pressure is 2kgf/cm ²(1.96 * 10 ⁵Pa).On the surface after the blasting treatment, mean roughness R _aBe 0.8 μ m.

(3) ungrease treatment

Make in its degreasing bath that impregnated in 30 ℃ of liquid temperature 30 seconds, remove the oil content on surface with degreaser.Then, wash processing, jet, remove moisture.

(4) electrolytic treatments

In the electrolyte of 50 ℃ of the liquid temperature that contains chromic acid 300g/L, sulfuric acid 2g/L, iron 1g/L, apply DC current continuously, be that anode is at current density 30A/dm with the roller ²Under carry out electrolytic treatments.The electric weight of electrolytic treatments is 10000C/dm ²

Current waveform carries out three phase full wave rectification, and using in addition and making the ripple composition by filter circuit is direct current below 5%.Polarity uses plumbous.Roller is vertically placed electrolyte, and cylindric configuration lead electrode is so that surround around it.Shelter processing so that the rotating shaft of pair roller does not partly carry out electrolytic treatments with vinyl chloride.

(5) chromium plating is handled

Then, in the electrolyte of 50 ℃ of the liquid temperature that contains chromic acid 300g/L, sulfuric acid 2g/L, iron 1g/L, applying DC current continuously, is that negative electrode is at current density 40A/dm with the roller ²Under carry out electroplating processes.Setting the electroplating processes time, is 6 μ m so that make electroplating thickness.

Current waveform carries out three phase full wave rectification, and using in addition and making the ripple composition by filter circuit is direct current below 5%.Polarity uses plumbous.Roller is vertically placed electrolyte, and cylindric configuration lead electrode is so that surround around it.Shelter processing so that the rotating shaft of pair roller does not partly carry out electrolytic treatments with vinyl chloride.

2. the manufacturing of aluminium sheet

Use contains each composition (quality %) shown in the 1st table, and the aluminium alloy modulation motlten metal that remainder is made up of Al and inevitable impurity after carrying out melt process and filtering, is made the ingot casting of thick 500mm, wide 1200mm of the DC casting.Thickness according to average 10mm uses flush cut machine cutting surface, and under 550 ℃, about 5 hours of soaking also keeps, even reduce to 400 ℃ of temperature, also can use hot-rolling mill to form the milled sheet of thick 2.7mm then.In addition, use the continuous annealing machine after heat-treating under 500 ℃, carry out cold rollingly, fine finishining is thick 0.3mm, wide 1060mm, thereby obtains aluminium sheet 1～3.

In addition, in cold rolling,, also use respectively the method identical, obtain aluminium sheet 4～6 respectively with aluminium sheet 1～3 except using aluminium sheet embossing finishing by above-mentioned acquisition with the roller.

Table 1

Aluminium sheet	Si	Fe	Cu	Mn	Mg	Cr	Zn	Ti
									1	0.080	0.300	0.001	0.001	0.000	0.001	0.003	0.021
2	0.076	0.270	0.023	0.001	0.000	0.001	0.003	0.021
									3	0.278	0.413	0.201	0.892	0.783	0.022	0.122	0.034

3. the making of support body for lithographic plate printing plate

(embodiment 1-1～embodiment 1-38, embodiment 3-1～3-7, embodiment 3-9, comparative example 1-1～1-2)

To be provided in surface treatment shown below by the aluminium sheet of above-mentioned acquisition, thereby obtain to be shown in each support body for lithographic plate printing plate in the 2nd table.

＜surface treatment 〉

Surface treatment is undertaken by the various processing of carrying out following (a)～(g) continuously.

(a) corrosion treatment in aqueous alkali (the 1st corrosion treatment)

On aluminium sheet, spray the aqueous solution of 60 ℃ of caustic soda concentration 370g/L, aluminium ion concentration 100g/L, temperature from playpipe, carry out corrosion treatment.Aluminium sheet after carry out the face of electrochemistry asperities processing etching extent be 3g/m ²

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.

(b) abatement processes in the acidic aqueous solution (the 1st abatement processes)

On aluminium sheet, spray the aqueous solution of 50 ℃ of sulfuric acid concentration 170g/L, aluminium ion concentration 50g/L, temperature by playpipe, carry out 5 second abatement processes.As aqueous sulfuric acid, use the waste liquid of (f) described later anodized operation.

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.

(c) use the electrochemistry asperities processing (processing of electrochemistry asperities) that exchanges in the acidic aqueous solution

As electrolyte, use the aqueous solution (35 ℃ of temperature) of the chloride ion concentration shown in the 2nd table, nitrate ion concentration, aluminium ion concentration, pH, control electric current by the transformer that has used the IGBT element, use can produce the power supply of the interchange of random waveform, and the aluminium sheet of having implemented (b) processing is carried out the processing of electrochemistry asperities.

In addition, chloride ion concentration uses hydrochloric acid and/or aluminium chloride to adjust, and nitrate ion concentration uses nitric acid to adjust, and aluminium ion concentration uses aluminium chloride to adjust.

The waveform of the electric current that uses in addition,, the frequency when the electric current of the rise time of waveform during as trapezoidal wave, use, electric weight, current ratio are respectively as shown in the 2nd table.Also have, electric weight is the electric weight summation of aluminium sheet when being anode, and current ratio is the ratio of the electric weight summation of the electric weight summation of aluminium sheet when being negative electrode when being anode with aluminium sheet.

In addition, exchange when crest and the current density of aluminium sheet when being anode is 50A/dm ²In addition, energy rate (duty) is 0.5.

The concentration control of electrolyte can be according to the tables of data of obtaining in advance, add chloride ion, nitrate ion and water with the proportional amount of conducting amount, carry out the multicomponent measurement of concetration with the capillary electrophoresis analysis method, from this result, the method for the addition of using compensation chloride ion, nitrate ion and water.

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.

(d) corrosion treatment in aqueous alkali (the 2nd corrosion treatment)

On aluminium sheet, spray the aqueous solution of 35 ℃ of caustic soda concentration 50g/L, aluminium ion concentration 5g/L, temperature by playpipe, carry out corrosion treatment.Aluminium sheet after carry out the processing of electrochemistry asperities face etching extent as the 2nd the table as shown in.

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.

(e) abatement processes in acidic aqueous solution (the 2nd abatement processes)

On aluminium sheet, spray the aqueous solution of 50 ℃ of sulfuric acid concentration 170g/L, aluminium ion concentration 5g/L, temperature by playpipe, carry out 5 second abatement processes.As aqueous sulfuric acid, use the waste liquid of (f) described later anodized operation.

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.

(f) anodized

As electrolyte, use aluminum sulfate to be dissolved in the 170g/L aqueous sulfuric acid and make the electrolyte (temperature 50 ℃) of aluminium ion concentration as 5g/L.Carry out anodized, so that the average current density that aluminium sheet carries out during the anode reaction is 15A/dm ², final oxide film thereon amount is 2.7g/m ²

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.

(g) hydrophilicity-imparting treatment

Make aluminium sheet impregnated in 10 seconds in the sodium metasilicate 1 quality % aqueous solution (20 ℃ of temperature).The Si amount of the surface of aluminum plate of measuring with fluorescent x-ray analysis apparatus is 3.5g/m ²

Then, carry out mangle, in addition, use to have playpipe that injection water diffuses into fan-shaped injection sheet and carry out washing in 5 seconds and handle, carry out mangle with niproll again with niproll.In addition, the wind that sprays 90 ℃ makes its drying 10 seconds, obtains support body for lithographic plate printing plate.

(embodiment 2-1～2-4, embodiment 3-8)

Carry out following (z) before at above-mentioned (a), in above-mentioned (a), make aluminium sheet after carry out the face of electrochemistry asperities processing etching extent be 10g/m ², in addition, use the method identical with embodiment 1-1～embodiment 1-38, obtain to be shown in embodiment 2-1～2-4 in the 2nd table and 3-8 support body for lithographic plate printing plate.

(z) mechanical asperities processing

Use device as shown in Figure 6, on one side the suspension of grinding agent (float stone) and water (proportion 1.12) is offered surface of aluminum plate as grinding milk, the roller shape nylon bruss with rotation carries out mechanical asperities processing on one side.In Fig. 6, the 1st, aluminium sheet, 2 and 4 is roller shape brushes, the 3rd, grinding milk, 5,6,7 and 8 is backing rolls.The average grain diameter of grinding agent is 30 μ m.The material of nylon bruss is 610 nylon, and staple length is 50mm, and the diameter of hair is 0.3mm.Nylon bruss is boring and closely carry out flocking and form on the tube of the stainless steel of φ 300mm.Rotating brush uses 3.The distance of two backing rolls (φ 200mm) of brush bottom is 300mm.The direction of rotation of brush is identical with the moving direction of aluminium sheet.The rotating speed of brush is 200rpm.The R of machinery asperities processing _aBe 0.45 μ m.

4. the observation on support body for lithographic plate printing plate surface

With scanning electron microscope (JSM-5500, NEC's corporate system.Below identical) in the surface configuration of observing resulting each support body for lithographic plate printing plate in embodiment 1-1～1-38, embodiment 2-1～2-4, embodiment 3-1～3-9 under 50000 times the enlargement ratio, the result is evenly and densely generated diameter 0.01～0.5 μ m on its surface fine concavo-convex.In addition, observe under 2000 times enlargement ratio with scanning electron microscope, the result has generated the concavo-convex of diameter 1～5 μ m on the surface of these support body for lithographic plate printing plate.The concavo-convex overlapping generation of fine concavo-convex and diameter 1～5 μ m of diameter 0.01～0.5 μ m.In addition, diameter 1～5 μ m's is concavo-convex not overlapping usually, generate independently, and evenly.

In contrast, observe the surface configuration of the support body for lithographic plate printing plate that in comparative example 1～2, obtains equally, the result has generated fine concavo-convex and diameter 1～5 μ m concavo-convex of diameter 0.01～0.5 μ m in its surface, but the situation of the concavo-convex and embodiment of diameter 1～5 μ m is compared, most peripheral parts overlap each other, and are inhomogeneous.

5. the making of original edition of lithographic printing plate

On above-mentioned resulting each support body for lithographic plate printing plate, the image recording layer that thermal positive type is set as described below obtains original edition of lithographic printing plate.In addition, before image recording layer is set, priming coat is set as described later.

The primary coat liquid of the following composition of coating on support body for lithographic plate printing plate 80 ℃ of following dry 15 seconds, forms filming of priming coat.The overlay capacity of dried coating is 15mg/m ²

＜primary coat liquid is formed 〉

Following macromolecular compound 0.3g

Methyl alcohol 100g

Water 1g

[Chemical formula 1]

Molecular weight 2.8 ten thousand

In addition, modulate the heat-sensitive layer coating fluid of following composition, be provided with on the support body for lithographic plate printing plate of priming coat, according to being coated with this heat-sensitive layer coating fluid and making its dried coating weight (heat-sensitive layer coating weight) be 1.8g/m ², make its dry formation heat-sensitive layer (image recording layer of thermal positive type), thereby obtain original edition of lithographic printing plate.

＜heat-sensitive layer coating fluid is formed 〉

Novolac resin (metacresol/paracresol=60/40, weight average molecular weight 7,000 contain unreacted cresols 0.5 quality %) 0.90g

EMA/isobutyl methacrylate/methacrylic acid copolymer (mol ratio 35/35/30) 0.10g

The anthocyanin dye A 0.1g that represents with following structural formula

Tetrahydrobenzene dicarboxylic acid anhydride 0.05g

P-methyl benzenesulfonic acid 0.002g

The equilibrium ion that makes ethyl violet is the material 0.02g of 6-hydroxyl-β-naphthalene sulfonic acids

Fluorine is surfactant (メ ガ Off ァ Star Network F-780F, big Japanese ink chemical industrial company system, solid constituent 30 quality) 0.0045g (solid constituent conversion)

Fluorine is surfactant (メ ガ Off ァ Star Network F-781F, big Japanese ink chemical industrial company system, solid constituent 100 quality %) 0.035g

Methyl ethyl ketone 12g

[Chemical formula 2]

Anthocyanin dye A

6. the evaluation of original edition of lithographic printing plate

The anti-brush of lithographic plate, stain resistance and luminously estimate in accordance with the following methods.

(1) anti-brush

Trend Setter with the Creo corporate system carries out decent the describing of figure to the original edition of lithographic printing plate that obtains under drum rotation speed 150rpm, beam (beam) intensity 10W.

Afterwards, with the PS プ ロ セ Star サ-940H of Fujiphoto (strain) system of the alkaline developer that following composition is housed, be to develop under 30 ℃, 20 seconds condition of developing time keeping the liquid temperature, obtain lithographic plate.In addition, any one original edition of lithographic printing plate Turin sensitivity is good.

＜alkaline developer is formed 〉

D-D-sorbite 2.5 quality %

NaOH 0.85 quality %

Polyethylene glycol lauryl ether (weight average molecular weight 1000) 0.5 quality %

Water 96.15 quality %

リ ス ロ Application printing machine with little gloomy コ-Port レ-シ ョ Application corporate system, use the printing ink of DIC-GEOS (N) China ink of big Japanese ink chemical industrial company system that resulting lithographic plate is printed, the printing number when beginning attenuation by all images concentration with Visual Confirmation is estimated anti-brush.

The result is as shown in the 2nd table.The implication of the symbol in the 2nd table is as described below.

More than A:30000 opens

A-B:20000 opens above but less than 30000

B:10000 opens above but less than 20000

Below C:10000 opens.

(1) stain resistance

The same during with the evaluation of above-mentioned (1) anti-brush, the lithographic plate that use obtains, with the ダ イ ヤ of Mitsubishi type F2 printing machine (Mitsubishi Heavy Industries's system), use the red printing ink of DIC-GEOS (s) to print, print the pollution condition of the blanket (blanket) after 10,000 with visual valuation.

The result is as shown in the 2nd table.The implication of the symbol in the 2nd table is as described below.

A: blanket is almost pollution-free

A-B: blanket has point pollution a little

B: blanket pollutes in allowed band

C: blanket pollutes, and printed article obviously pollutes

(3) luminous

To be installed on the リ ス ロ Application printing machine of little gloomy コ-Port レ-シ ョ Application corporate system with the lithographic plate that obtains by the identical method of the evaluation of above-mentioned (1) anti-brush, the quantity delivered that damping water is drawn on one side in, the luminous situation of the non-image portion of the space of a whole page of visualization on one side, the quantity delivered of the dumping processing solution when using beginning luminous are estimated luminous (observing the easy degree of the shinny state of the space of a whole page).

The result is as shown in the 2nd table.The implication of the bis in the 2nd table is as described below.

A: when drawing damping water in, the space of a whole page is difficult to luminous

B: when drawing damping water in, the space of a whole page is easy to luminous, and the adjustment of visual damping water down is difficulty a little a bit.

As knowing clearly by the 2nd table, use is by the lithographic plate of the support body for lithographic plate printing plate of manufacture method (embodiment 1-1～1-38, embodiment 2-1～2-4, embodiment 3-1～3-9) acquisition of support body for lithographic plate printing plate of the present invention, anti-brush and stain resistance are all outstanding, in addition, luminous also outstanding.

In addition, when forming when concavo-convex (embodiment 1-1～1-18, embodiment 1-37, embodiment 3-5) before the 1st corrosion process by crimping aluminium sheet embossing finishing with roller on the surface and forming (embodiment 2-1～2-4, embodiment 3-8) when concavo-convex on the surface by carrying out mechanical asperities processing before the 1st corrosion process, the lithographic plate of the support body for lithographic plate printing plate that use obtains, it is luminous also outstanding especially.

In contrast, with regard to the too much comparative example 1-1 of the electric weight summation when aluminium sheet is anode in the processing of electrochemistry asperities, use the low contamination resistance of the lithographic plate of the support body for lithographic plate printing plate that obtains.

In addition, with regard to the too high comparative example 1-2 of pH of the aqueous solution that is used for the processing of electrochemistry asperities, the pit of the support body for lithographic plate printing plate that obtains disperses insufficient, pit is big or small inhomogeneous in addition, since formed big recess, thus low contamination resistance, anti-brush and luminous also poor.

Claims (5)

1. the manufacture method of a support body for lithographic plate printing plate, it is in the aqueous solution that contains chloride ion and nitrate ion at least, the electric weight summation when aluminium sheet is applied alternating current and makes described aluminium sheet be anode is 100～300C/dm ², carry out the processing of electrochemistry asperities, obtain support body for lithographic plate printing plate, chloride ion concentration is 8～50g/L in the described aqueous solution, nitrate ion concentration is 0.8～6g/L.

2. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1, wherein,

The described aqueous solution contains hydrochloric acid and nitric acid.

3. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1 or 2, wherein,

The pH of the described aqueous solution is below 0.8.

4. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1, wherein,

The described aqueous solution contains the above aluminium ion of 2g/L.

5. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1, wherein,

Described aluminium sheet has concavo-convex printed words from the teeth outwards.

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