CN100446993C - Method for manufacturing support body for lithographic plate and its support body - Google Patents

Abstract

This method manufactures the support for the lithographic printing plate using an aluminum sheet with an unevenness formed on the surface by transferring an uneven pattern, through treatments such as (1) electrochemical surface roughing in an aqueous nitric acid solution, (2) electrochemical surface roughing in an aqueous hydrochloric acid solution and (3) anodic oxidation.

Description

The manufacture method of support body for lithographic plate printing plate and original edition of lithographic printing plate

Technical field

The present invention relates to the manufacture method of support body for lithographic plate printing plate.Particularly, relate to be used for the manufacture method of the support body for lithographic plate printing plate of all good original edition of lithographic printing plate of sensitivity, pollution resistance and anti-seal.

Background technology

The lithographic printing plate-use aluminum support (below, be called for short " support body for lithographic plate printing plate ") that is used for lithographic plate is by aluminium sheet being implemented the asperities processing and other surface treatment is made.As the method for asperities processing, the known processing method that mechanical asperities processing, the processing of electrochemistry asperities (below be also referred to as " processing of electrolysis asperities "), chemical asperities processing (chemical corrosion method) is for example arranged and make up them.

Wherein, mechanical asperities processing is more effective for the anti-seal that improves lithographic plate.As mechanical asperities processing, general known is to spray the method for grinding agent slip between nylon bruss that rotates and aluminium sheet.

, this uses the method for nylon bruss and grinding agent, can be at a high speed and carry out the advantage of asperitiesization at an easy rate though have, and shortcoming is that the control of granularity of grinding agent is difficult, when the bigger grinding agent of particle diameter is sneaked into, produces dark recess easily in the part.Its result, when there is dark recess in the surface local ground of support body for lithographic plate printing plate, in the lithographic plate that is provided with the eurymeric image recording layer, the part that non-image portion takes place is difficult to video picture than the deep branch problem.In addition, in the lithographic plate of the image recording layer that is provided with minus, the part that image portion takes place is difficult to form the problem of image than the deep branch.

In addition, use the method for nylon bruss and grinding agent,, will produce sharp-pointed part, therefore, need in the caustic corrosion of back operation is handled, aluminium be dissolved in large quantities for this part is become smoothly owing to be the asperities processing of physics.So the expense height is arranged, and problem big to the influence of environment.

Particularly, what patent documentation 1 was put down in writing is such galley, promptly, having average diameter is 10～16 μ m, be preferably 20～24 μ m pit surface structure and handle through roller process and mold pressing after aluminum support on, by the recessed fine structure in the hole with the recessed diameter in hole in 0.1～6 mu m range of electrochemistry asperities processing manufacturing on this surface the textural overlapping galley that forms.

What patent documentation 2 was put down in writing is, to comprise diameter is that 2～50 μ m and average diameter are the hemisphere impression of 20～30 μ m and the aluminium sheet of the pre-mint-mark of process, in the electrolyte of chloride that is selected from hydrochloric acid, nitric acid, sulfuric acid and aluminium salt or nitrate ion, carry out asperitiesization and the support body for lithographic plate printing plate that forms.Surface roughness Ra after the asperitiesization is even, and whole zone is 1.0～1.5 μ m.

What patent documentation 3 was put down in writing is, use the calendering cylinder by transfer printing with the aluminium sheet asperitiesization, the preprocessing layer that is formed by acrylic acid, methacrylate, organophosphor based polymer or their copolymer is set in the above, and the original edition of lithographic printing plate that the cohesive of preprocessing layer and photosensitive layer is improved.

The method that above-mentioned conventional art is put down in writing is compared with the asperities method of using nylon bruss and grinding agent, and generation is concavo-convex uniformly easily, still, the shortcoming of anti-seal poor performance is arranged greatly because of its concavo-convex pit.

Patent documentation 1

The spy opens the 2002-240448 communique

Patent documentation 2

Special by the 2002-38300 communique

Patent documentation 3

The WO02/19032 communique

Summary of the invention

Therefore, press for the problem that there is dark recess in aforesaid part, the method that sensitivity, pollution resistance, anti-seal are improved of solving.

The objective of the invention is to solve existing problem in the above-mentioned conventional art, provide easily to obtain concavo-convexly uniformly, and can obtain the support body for lithographic plate printing plate (the following support that only is called sometimes) and the manufacture method thereof of sensitivity, pollution resistance, the well behaved original edition of lithographic printing plate of anti-seal.

Present inventors find, use has formed concavo-convex aluminium sheet through the transfer printing relief pattern and on the surface, carry out the electrochemistry asperities processing of at least 2 operations, can obtain to form the support body for lithographic plate printing plate of all good lithographic plate of sensitivity, pollution resistance, pressrun.

Promptly the invention provides following [1]～[7].

[1] a kind of manufacture method of support body for lithographic plate printing plate is characterized in that, uses and has formed concavo-convex aluminium sheet through the transfer printing relief pattern on the surface, carries out following processing successively:

(4) carry out the processing of electrochemistry asperities in the aqueous solution of nitric acid,

(5) carry out the processing of electrochemistry asperities in the aqueous hydrochloric acid solution,

(6) anodized.

[2] a kind of manufacture method of support body for lithographic plate printing plate is characterized in that, uses and has formed concavo-convex aluminium sheet through the transfer printing relief pattern on the surface, carries out following processing successively:

(10) carry out chemical attack in the alkaline aqueous solution and handle,

(11) carry out abatement processes in the acidic aqueous solution,

(12) carry out the processing of electrochemistry asperities in the aqueous solution of nitric acid,

(13) carry out chemical attack in the alkaline aqueous solution and handle,

(14) carry out abatement processes in the acidic aqueous solution,

(15) carry out the processing of electrochemistry asperities in the aqueous hydrochloric acid solution,

(16) carry out chemical attack in the alkaline aqueous solution and handle,

(17) carry out abatement processes in the acidic aqueous solution,

(18) anodized.

[3] a kind of manufacture method of support body for lithographic plate printing plate, it is characterized in that, and on the surface has formed concavo-convex aluminium sheet concavo-convex through the transfer printing relief pattern, the pit of overlapping average opening footpath 0.5～5 μ m pit and average opening footpath 0.05～0.3 μ m carries out anodized then or carries out anodized and hydrophilicity-imparting treatment.

[4] according to the manufacture method of each described support body for lithographic plate printing plate of described 1～3, wherein said formed concavo-convex aluminium sheet on the surface be the aluminium sheet that contains 0.020～0.2 quality %Cu.

[5] according to the manufacture method of each described support body for lithographic plate printing plate of described 1～4, the transfer printing of wherein said relief pattern is to carry out in the final calendering procedure of aluminium sheet manufacturing process.

[6] according to the manufacture method of each described support body for lithographic plate printing plate of described 1～5, after the wherein said anodized, further carry out hydrophilicity-imparting treatment.

[7] a kind of original edition of lithographic printing plate on described 1～6 the resulting support of each manufacture method, further has image recording layer.

According to the present invention, can provide the manufacture method of the support body for lithographic plate printing plate that can obtain all good original edition of lithographic printing plate of sensitivity, pollution resistance and Nai Yin.

Description of drawings

Fig. 1 is a pattern sectional view employed during the washing in the manufacture method of support body for lithographic plate printing plate of the present invention is handled, wash the device of processing by the liquid film that freely falls the curtain shape.

Fig. 2 is the figure of the example of employed, the ac power waveform figure of electrochemical asperities processing in the manufacture method of expression support body for lithographic plate printing plate of the present invention.

Fig. 3 is the side view of an example in the electrochemical asperities processing that exchanges of the use in the manufacture method of expression support body for lithographic plate printing plate of the present invention, the radial mode groove.

Fig. 4 is that the anodized in the manufacture method of support body for lithographic plate printing plate of the present invention is employed, the skeleton diagram of anodized device.

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

Among the figure: the 1-aluminium sheet, the 11-aluminium sheet, 12-is drum roller entad, 13a, the 13b-main pole, 14-electrolytic treatments liquid, 15-electrolyte supply mouth, the 16-slit, 17-electrolyte path, 18-impressed current anode, 19a, the 19b-IGCT, 20-AC power, 40-master's electrolytic cell, 50-impressed current anode groove, 100-washes the device of processing by the liquid film that freely falls the curtain shape, 102-water, the 104-water tank, 106-gives water drum, 108-rectification part, 410-anodized device, 412-gives electric groove, 413-medial launder, 414-anodized groove, 416-aluminium sheet, 418,426-electrolyte, the 420-anode, 422, the 428-deflector roll, 424-pinch roll, 430-negative electrode, the 434-dc source, 436,438-gives nozzle for liquid, 440-shield, 442-leakage fluid dram

The specific embodiment

Below, describe the present invention in detail.

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

＜aluminium sheet (calendering aluminium) 〉

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 to be principal component, and contain the alloy sheets of other element of trace.

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

Aforesaidly be used for aluminium sheet of the present invention, its composition is not particularly limited, can for example suitably utilize, the 4th plate (nineteen ninety of aluminium handbook, the distribution of light metal association) material known in the past of record in, as, the Al-Mn of JIS A1050, JIS A1100, JIS A1070, the JISA3004 that contains Mn, international login 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 the above-mentioned aluminium alloy is that alloy, Al-Mn-Mg are alloy (JIS A3005).Having, can also be that alloy, Al-Si are alloy with the Al-Zr that contains Zr, Si again.In addition, can be alloy also with Al-Mg-Si.

Have again, can also use UBC (Used BeverageCan) the ingot calendering of the aluminum beverage pot that dissolving is finished using and the aluminium sheet that obtains.

The employed aluminium sheet of the manufacture method of support body for lithographic plate printing plate of the present invention preferably contains Cu:0.020～0.2 quality %.When the Cu content of aluminium sheet is above-mentioned scope, in nitric acid alternating current electrolysis described later, can form bigger and uniform recess.Its result uses the lithographic plate of the support body for lithographic plate printing plate that is obtained by the present invention to have better anti-seal.

Cu content is considered aspect the uniform recess of generation (cellular pit) in nitric acid alternating current electrolysis described later, below the preferred 0.15 quality %, more preferably below the 0.12 quality %, most preferably below the 0.10 quality %.

Preferably the aluminium sheet composition is: below Si:0.07～0.09 quality %, Fe:0.20～0.29 quality %, the Mn:0.01 quality %, below the Mg:0.01 quality, below the Cr:0.01 quality %, below the Zn:0.01 quality, below the Ti:0.02 quality %, more than the Al:99.4 quality %.

Relevant JIS1050 material, the technology that is proposed by the applicant is documented in following each communique: the spy opens clear 59-153861 number, the spy opens clear 61-51395 number, the spy opens clear 62-146694 number, the spy opens clear 60-215725 number, the spy opens clear 60-215726 number, the spy opens clear 60-215727 number, the spy opens clear 60-216728 number, the spy opens clear 61-272367 number, the spy opens clear 58-11759 number, the spy opens clear 58-42493 number, the spy opens clear 58-221254 number, the spy opens clear 62-148295 number, Te Kaiping 4-254545 number, Te Kaiping 4-165041 number, special fair 3-68939 number, Te Kaiping 3-234594 number, spy fair 1-47545 number and spy open clear 62-140894 number.In addition, also put down in writing relevant technologies in special fair 1-35910 communique, the special public clear 55-28874 communique.

Relevant JIS1070 material, the technology that the applicant proposes is documented in following each communique: the spy open flat 7-81264 number, spy open flat 7-305133 number, spy open flat 8-49034 number, spy open flat 8-73974 number, the spy opens flat 8-108659 number and the spy opens flat 8-92679 number.

Relevant Al-Mg is an alloy, and the technology that the applicant proposes is documented in following each communique: special public clear 62-5080 number, special public clear 63-60823 number, special fair 3-61753 number, the spy opens clear 60-203496 number, the spy opens clear 60-203497 number, special fair 3-11635 number, the spy opens clear 61-274993 number, the spy opens clear 62-23794 number, the spy opens clear 63-47347 number, the spy opens clear 63-47348 number, the spy opens clear 63-47349 number, the spy opens clear 64-1293 number, the spy opens clear 63-135294 number, the spy opens clear 63-87288 number, special fair 4-73392 number, special fair 7-100844 number, the spy opens clear 62-149856 number, special fair 4-73394 number, the spy opens clear 62-181191 number, special fair 5-76530 number, the spy opens clear 63-30294 number and special fair 6-37116 number.In addition, the spy opens flat 2-215599 communique, the spy opens in the clear 61-201747 communique and also put down in writing relevant technologies.

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

Relevant Al-Mn-Mg is an alloy, and the technology that the applicant proposes is documented in the spy and opens in clear 62-86143 communique and the flat 3-222796 communique of Te Kai.In addition, special public clear 63-60824 number, spy are opened clear 60-63346 number, spy and are opened clear 60-63347 number, spy and open flat 1-293350 number 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.

Relevant Al-Zr is an alloy, and the technology that the applicant proposes is documented in special public clear 63-15978 communique and the clear 61-51395 communique of Te Kai.In addition, the spy opens clear 63-143234 number, spy and opens each communique of clear 63-143235 number and also put down in writing relevant technologies.

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

Make aluminium alloy become sheet material, can adopt method described as follows.At first,, carry out purified treatment according to well-established law to being adjusted to the molten aluminium alloy of given alloying component amount, and casting.During 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; Perhaps make up the processing method of 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 aforesaid purified treatment.The filtration treatment of relevant motlten metal is documented in following each communique: the spy opens flat 6-57432 number, spy and opens flat 3-162530 number, spy and open flat 5-140659 number, spy and open flat 4-231425 number, spy and open flat 4-276031 number, spy and open flat 5-311261 number, spy and open flat 6-136466 number.In addition, the degassing of relevant motlten metal is handled, and is documented in the spy and opens flat 5-51659 communique, real opening in the flat 5-49148 communique.The applicant opens in the flat 7-40017 communique the spy, has also provided the technology of the degassing of relevant motlten metal.

Below, use through the motlten metal of above-mentioned purified treatment and cast.Relevant casting method has with the method for the use solid casting mold of DC casting representative and drives the method for casting mold with the use of continuous casting process representative.

In the DC casting, be that 0.5～30 ℃/second scope is solidified in cooling velocity.If be lower than 1 ℃, might form thick intermetallic compound in a large number.When carrying out the DC casting, can make the ingot bar of thickness of slab 300～800mm.According to well-established law, this ingot bar is carried out flush cut as required, usually, the 1～30mm on cutting top layer, best 1～10mm.Before and after it, carry out evenly heating as required and handle.When carrying out the evenly heating processing, for fear of thickization of intermetallic compound, 450～620 ℃ of heat treatments of carrying out 1～48 hour.If heat treatment is lower than 1 hour, the effect that evenly heating is handled might be insufficient.In addition, when not carrying out the evenly heating processing, the advantage that can reduce cost is arranged.

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

Operation by above is configured as certain thickness, as the aluminium sheet of 0.1～0.5mm, can also further improve flatness by apparatus for correcting such as roll leveller, tension level(l)ers.The improvement of flatness can be cut into aluminium sheet the laggard row of sheet, but in order to improve productivity, be preferably under the continuous coiled material state and carry out.In addition, in order to be processed into certain plate width of cloth, can also make aluminium sheet pass through many shear lines of plate.Have again,, 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.Oil film can be suitable for volatile material and nonvolatile matter as required.

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 ァ Le ス ィ ス キ ャ ス -use salband of II type representative and the method for cooling block.When using continuous casting process, be that 100～1000 ℃/second scope is solidified in cooling velocity.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 3-79798 number, spy and opens flat 5-201166 number, spy and open flat 5-156414 number, spy and open flat 6-262203 number, spy and open flat 6-122949 number, spy and open flat 6-210406 number, spy and open flat 6-26308 number.

When casting continuously, for example use the method with chill roll of hunter method etc., can be directly, cast the cast sheet of thickness of slab 1～10mm continuously, have the advantage that can omit hot-rolled process.In addition, use Hazelette method etc. with the method for salband the time, the cast sheet that can cast thickness of slab 10～50mm, after casting just finished, the configuration hot roll rolled continuously usually, can obtain the continuous casting calendering plate of thickness of slab 1～10mm.

Above-mentioned continuous casting calendering plate and DC casting similarly through the improvement of cold rolling, intermediate annealing, flatness, operation such as cut, can be shaped as for example thickness of slab of 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 6-220593 number, spy and open flat 6-210308 number, spy and open flat 7-54111 number, spy and open in each communique of flat 8-92709 number.

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

The aluminium sheet of Zhi Zaoing wishes to have following various characteristics as mentioned above.

The intensity of aluminium sheet is in order to obtain as the necessary stiffness of support body for lithographic plate printing plate, more than the preferred 120MPa of 0.2% proof stress.Have, required stiffness to a certain degree when handling in order to obtain to carry out burning (burning) is more than the 0.2% proof stress preferred 80MPa of 270 ℃ of heat treated after 3～10 minutes, more preferably more than the 100MPa again.During 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.The relevant technologies that the applicant proposes is documented in that the spy opens flat 7-126820 communique, the spy opens in the clear 62-140894 communique.

In addition, it is desirable to more, the aluminium sheet hot strength is 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 had better not be too thick on the surface.The crystalline structure of surface of aluminum plate, below the wide preferred 200 μ m, more preferably below the 100 μ m, most preferably below the 50 μ m, in addition, below the preferred 5000 μ m of the length of crystalline structure, more preferably below the 1000 μ m, most preferably below the 500 μ m.The relevant technologies that the applicant proposes is documented in the spy and opens flat 6-218495 number, spy and open flat 7-39906 number, spy and open in each communique of flat 7-124609 number.

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 surface distributed inhomogeneous.The relevant technologies that the applicant proposes is documented in the spy and opens flat 6-48058 number, spy and open flat 5-301478 number, spy and open in each communique of flat 7-132689 number.

The size of the intermetallic compound of aluminium sheet and density might exert an influence to chemical asperities processing and the processing of electrochemistry asperities.The relevant technologies that proposes about this problem the applicant is documented in the spy and opens flat 7-138687 number, spy and open in each communique of flat 4-254545 number.

Aluminium sheet used in the present invention can use in advance and form concavo-convex aluminium sheet through the transfer printing relief pattern on the surface, also can form concavo-convex by the transfer printing relief pattern on aluminium sheet.It is unqualified to be processed to form concavo-convex operation by calendering, and the preferred calendering cylinder that uses rolls processing.Also can make aforesaid aluminium sheet in its final calendering procedure, form concavo-convex back by lamination calendering, transfer printing etc. and use.

Wherein, preferable methods is: and regulate the cold rolling, perhaps together cold rolling of final thickness of slab with the fine finishining of the adjusted surface configuration of the final thickness of slab of fine finishining, male and fomale(M﹠F) is crimped on the aluminium sheet, the transfer printing concaveconvex shape makes the surface of aluminium sheet form concaveconvex structure.Specifically can be suitable for the spy and open the method for putting down in writing in the flat 6-262203 communique.

By using the surface to have the aluminium sheet of concaveconvex structure, 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, acquisition is concavo-convex uniformly easily, and can obtain sensitivity, pollution resistance, all good original edition of lithographic printing plate of anti-seal.

The final cold rolling process that transfer printing is preferably in common aluminium sheet carries out.The most handy 1～3 circulation of calendering that is used for transfer printing is carried out, and divides other reduction ratio preferred 3～8%.

Among the present invention, the surface that obtains to be used for concavo-convex transfer printing has the method for concavo-convex transfer platen, use be the method for the given aluminum particulate of spraying, wherein 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 given particle diameter is just passable.Sand grains uses hard and each angle particle when being the aluminium oxide particles of acute angle, makes 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.When being set at above-mentioned scope, can obtain as the enough big surface roughness of transfer platen, using this transfer platen to be paid concavo-convex surface of aluminum plate so also has enough big roughness.And, can make the pit number become abundant.

In the air-jet method, preferably carry out 2～5 times and spray, wherein more preferably carry out 2 times.When carrying out spraying for 2 times, spray formed concavo-convex irregular protuberance the 1st time can prune, so the surface of being paid concavo-convex aluminium sheet with the calendering cylinder that obtains is not easy to form the dark recess of part by the 2nd time injection.Its result, the video picture of lithographic plate (sensitivity) becomes good.

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

After carrying out air-jet method, preferably grind before handling up to the value of average surface roughness (Ra) after jet and descend till 10～40% carrying out plating described later.Grind preferred sand paper, grinding stone or the polishing wheel of using.Become neatly by the height that grinds the protuberance that can make the transfer platen surface, its result uses this transfer platen to be paid concavo-convex surface of aluminum plate and is not easy to form local dark concave portion.Thereby the video picture 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.

The material of transfer platen is not particularly limited, and can use for example known calendering cylinder material.

The preferred cylinder that uses steel among the present invention.Wherein more satisfactory by the cylinder of casting manufacturing.The example that desirable 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 common conduct rolls tool steel (SKD), high-speed steel (SKH), the high-carbon-chromium bearing steel (SUJ) of cylinder use, contains as the carbon of alloying element and the forged steel of chromium and molybdenum and vanadium Huang.In order to obtain the long cylinder life-span, can use the high-chromium alloy cast-iron that contains 10～20 quality % chromium.

Wherein, the preferred cylinder of making by casting that uses.At this moment, the hardness Hs preferred 80～100 after quenching, the tempering.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 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.Hard chrome plating can adopt as industrial hard chrome plating method well-known use CrO in the past ₃-SO ₄Bath, CrO ₃-SO ₄-fluoride bath etc. are based on electric plating method.

Preferred 3～15 μ m of the thickness of hard chrome plating film, more preferably 5～10 μ m.When being set at above-mentioned scope, be not easy to take place the plated film part and come off promptly to electroplate from the interface of cylinder surface material and plated film and peel off, and the raising effect of abrasion performance being also obvious.The thickness of hard chrome plating film can be regulated by adjusting the electroplating processes time.

Obtain the surface and have the method for concavo-convex calendering cylinder, can use the method that is documented in the following communique: the spy open clear 60-36195 number, spy open 2002-251005 number, spy open clear 60-203495 number, the spy opens clear 55-74898 number and the spy opens clear 62-111792 number.

Use the surface to have the aluminium sheet that concavo-convex calendering cylinder has formed relief pattern, preferably adopt to have the concavo-convex at interval structure of 10～100 μ m on the surface.

At this moment, preferred 0.4～1.5 μ m of arithmetic mean surface roughness (Ra), more preferably 0.4～0.8 μ m.Preferred 1～6 μ m of Rmax, more preferably 2～5 μ m.In addition, preferred 5～150 μ m of Rsm, more preferably 10～100 μ m.

The recess number on surface, preferred 200～20000/mm are arranged again ²

The present invention uses, and to have formed concavo-convex aluminium sheet through the transfer printing relief pattern on the surface be continuous band-shaped 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 corresponding big or small sheet-fed shape of the original edition of lithographic printing plate of goods listing.

The scar of surface of aluminum plate might become defective when being processed into support body for lithographic plate printing plate, therefore, in the last stage of the surface treatment procedure of making support body for lithographic plate printing plate, must be with the alap limit of being controlled at of scar.So it is more satisfactory to be not easy abrasive container dimensions when having stable morphology and carrying.

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

The aluminium sheet that the present invention uses thick is 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 the size of printing machine, galley and user's hope.

＜surface treatment 〉

The manufacture method of support body for lithographic plate printing plate of the present invention is to use through the transfer printing relief pattern and on the surface and has formed concavo-convex aluminium sheet, implements the manufacture method of the following support body for lithographic plate printing plate of handling,

(1) carry out electrochemical asperities processing (below be also referred to as " nitric acid alternating current electrolysis ") in the aqueous solution of nitric acid,

(2) carry out electrochemical asperities processing (below be also referred to as " hydrochloric acid alternating current electrolysis ") in the aqueous hydrochloric acid solution,

(3) anodized.

In the manufacture method of support body for lithographic plate printing plate of the present invention, can also contain above-mentioned various operations in addition.

In addition, before and after the processing of described (1), (2), can also carry out corrosion treatment (below be also referred to as " caustic corrosion processing ") in the aqueous alkali and the abatement processes in the acidic aqueous solution (below be also referred to as " abatement processes ").

Preferable methods wherein, be that aluminium sheet is implemented that first caustic corrosion processing, first abatement processes, nitric acid alternating current electrolysis, second caustic corrosion processing, second abatement processes, hydrochloric acid alternating current electrolysis, the 3rd caustic corrosion are handled, after the 3rd abatement processes and the described anodized, further implemented hydrophilicity-imparting treatment according to following order at least.

The Grains shape on＜surface 〉

The asperities formation method of the support that obtains with manufacture method of the present invention is, and on the surface has formed concavo-convex aluminium sheet concavo-convex through the transfer printing relief pattern, second pit of first pit of average opening footpath 0.5～5 μ m and average opening footpath 0.05～0.3 μ m is further overlapping, afterwards, carry out anodized.Can also carry out hydrophilicity-imparting treatment again.

Among the present invention, first pit of average opening footpath 0.5～5 μ m mainly keeps image recording layer by the effect of casting anchor, and has the function of the pressrun of paying.If the average opening of pit footpath is lower than 0.5 μ m, and the adhesiveness that is arranged between the image recording layer on upper strata might descend the anti-seal decline of lithographic plate.And the average opening of pit is when directly surpassing 5 μ m, and the quantity of the pit interface portion of the performance effect of casting anchor reduces, and so anti-seal also may descend.

Second pit that overlaps average opening footpath 0.05～0.3 μ m on the described pit mainly works to improve pollution resistance.By first pit of combination average opening footpath 0.5～5 μ m and second pit of average opening footpath 0.05～0.3 μ m, when lithographic plate provided damping water, its surface can form uniform moisture film during printing, suppressed the generation of the pollution of non-image portion.If the average opening footpath of second pit is lower than 0.05 μ m, might form moisture film does not have positive effect.And the average opening of pit is when directly surpassing 0.3 μ m, and first pit of 0.5～5 μ m may be destroyed, and can not obtain the effect of the above-mentioned anti-seal raising that this pit brought.

Below, each operation of surface-treated is elaborated.

＜mechanical asperities processing 〉

Among the present invention, can use brush and grinding-material to carry out the asperities processing of machinery, also can not carry out, preferably use brush and grinding-material to carry out the asperities processing of machinery.Before the preferred electrochemical asperities processing of time that the asperities processing of machinery is carried out.The surface area of the asperities processing aluminium sheet by machinery increases.

At first, before the surface roughening that aluminium sheet is utilized brush was handled, the ungrease treatment of as required aluminium sheet being removed surperficial rolling oil was for example carried out ungrease treatment with surfactant, organic solvent or alkaline aqueous solution etc.But rolling oil adheres to more after a little while can omit ungrease treatment.

Then, with a kind or at least 2 kinds of different brushes of mao footpath, on one side the abrasive slurries are supplied with the surface roughening processing that surface of aluminum plate is utilized brush on one side.The asperities processing of relevant machinery is opened in flat 6-135175 communique, the special public clear 50-40047 communique the spy and is documented.The brush cylinder can leave flat 6-135175 communique as the spy and make up the different brush cylinder in hair footpath putting down in writing.

＜the first caustic corrosion is handled 〉

Caustic corrosion is handled, and is that above-mentioned aluminium sheet is contacted with aqueous slkali, dissolves the processing on top layer.

The purpose that first caustic corrosion of carrying out before the nitric acid alternating current electrolysis is handled is to form uniform recess by the nitric acid alternating current electrolysis, and remove the surperficial rolling oil of aluminium sheet (calendering aluminium), dirt, natural oxide film etc.

During first caustic corrosion is handled, the preferred 0.1g/m of etching extent ²More than, more preferably 0.5g/m ²More than, 1g/m most preferably ²More than, and, preferred 10g/m ²Below, more preferably 8g/m ²Below, further preferred 5g/m ²Below, 3g/m most preferably ²Below.Etching extent in the nitric acid alternating current electrolysis, might can not generate uniform pit very little the time, and produces spot.On the other hand, when etching extent was too many, the use amount of aqueous alkali increased, and is uneconomical economically.

As the alkali that is used for aqueous slkali, can list: caustic alkali, alkali metal salt.Particularly, as caustic alkali, for example: caustic soda, caustic potash.In addition, as alkali metal salt, for example: alkali silicates such as sodium polysilicate, sodium metasilicate, positive potassium silicate, potassium silicates; 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, tribasic sodium phosphate, three generations's potassium 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.

During first caustic corrosion is handled, more than the preferred 30g/L of the concentration of aqueous slkali, more preferably more than the 300g/L, and below the preferred 500g/L, more preferably below the 450g/L.

In addition, aqueous slkali preferably contains aluminium ion.More than the preferred 1g/L of aluminium ion concentration, more preferably more than the 50g/L, and below the preferred 200g/L, more preferably below the 150g/L.Aforesaid aqueous slkali, for example, can water and the caustic soda aqueous solution and the sodium aluminate of 48 quality % modulate.

During first caustic corrosion was handled, the temperature of aqueous slkali was preferred more than 30 ℃, more preferably more than 50 ℃, and also preferred below 80 ℃, more preferably below 75 ℃.

During first caustic corrosion was handled, the processing time was preferred more than 1 second, more preferably more than 2 seconds, and also preferred below 30 seconds, more preferably below 15 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, keep certain amount of liquid 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 %.

Conductivity meter and densimeter preferably use the meter that passes through temperature-compensating respectively.Densimeter preferably uses differential pressure type.

As the method that aluminium sheet is contacted with aqueous slkali, can be listed below: 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 according to 10～50mm, more satisfactory with the method for the amount spraying corrosive liquid of per 1 playpipe 10～100L/min.Playpipe preferably is set at many.

After the caustic corrosion processing finished, the most handy pinch roll was removed corrosive liquid, and then after carrying out washing in 1～10 second, further used pinch roll (niproller) to remove corrosive liquid.

Washing is handled, and preferably uses the device of washing processing by the liquid film that freely falls the curtain shape to wash, 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 the device 100, water 102 is given water pot 104 by supplying with for water drum 106, and when water 102 overflowed from giving water pot 104, through the rectification part rectification, the liquid film that freely falls the curtain shape was supplied to aluminium sheet 1.During operative installations 100, the preferred 10～100L/min of liquid measure.In addition, the distance L that the water 102 between device 100 and the aluminium sheet 1 exists as the liquid film that freely falls the curtain shape, preferred 20～50mm.Have, the angle [alpha] of aluminium sheet is with respect to horizontal direction again, preferred 30～80 °.

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 by the liquid film of free-falling curtain shape, it is more satisfactory for example to be documented in the device that the spy opens in the 2003-96584 communique.

In addition, employed playpipe is handled in washing, for example can use, and injection water diffuses into fan-shaped injection sheet a plurality of playpipes on the width of aluminium sheet.Spray the preferred 20～100mm in interval of sheet, and, per 1 preferred 0.5～20L/min of liquid measure that sprays sheet.Playpipe preferably uses many.

＜the first abatement processes 〉

After carrying out first caustic corrosion processing,, preferably implement pickling (first abatement processes) for the dirt (dirt) of removing remained on surface.Abatement processes is undertaken by aluminium sheet is contacted with acid solution.

The acid of using can list: nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, boron hydrogen fluoride etc.

First caustic corrosion is handled in first abatement processes of being carried out the back, preferably uses the waste liquid that overflows of the employed electrolyte of nitric acid alternating current electrolysis that carries out below.

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 first abatement processes, preferably use and contain the acid of 1～400g/L and the aluminum ions acid solution of 0.1～5g/L.

The temperature of acid solution is preferred more than 20 ℃, more preferably more than 30 ℃, and also preferred below 70 ℃, more preferably below 60 ℃.

In first abatement processes, the processing time is preferred more than 1 second, more preferably more than 4 seconds, and also preferred below 60 seconds, more preferably below 40 seconds.

As the method that aluminium sheet is contacted with acid solution, can be listed below: 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 preferably is set at many.

After abatement processes finished, the most handy pinch roll was removed liquid, after carrying out washing for 1～10 second, further removed liquid with pinch roll.

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

In addition, in first abatement processes, as abatement processes liquid, the employed electrolyte of nitric acid alternating current electrolysis that use is carried out below overflow waste liquid the time, after the abatement processes, preferably do not carry out removing the processing and the washing processing of liquid, make surface of aluminum plate keep not dried state with pinch roll, spray suitable treatment fluid as required on one side, Yi Bian handle aluminium sheet up to nitric acid alternating current electrolysis operation.

＜nitric acid alternating current electrolysis 〉

The nitric acid alternating current electrolysis is the electrochemical asperities processing that the use in containing the aqueous solution of nitric acid exchanges.By the nitric acid alternating current electrolysis, can make surface of aluminum plate form suitable sag and swell.When aluminium sheet contains relatively large Cu, in the nitric acid alternating current electrolysis, form bigger and uniform recess.Its result uses the lithographic plate of the resulting support body for lithographic plate printing plate of the present invention to have good anti-seal.

The nitric acid alternating current electrolysis, can according to as special public clear 48-28123 communique, and the electrochemical surface roughening method described in the 896th, No. 563 specification of BP (electrolytic surface roughening method).This electrolytic surface roughening method is used sine-shaped alternating current, also can use the spy to open the special waveform described in the clear 52-58602 communique.In addition, can also use the spy to open the waveform described in the flat 3-79799 communique.Have, the spy opens clear 55-158298 number again, the spy opens clear 56-28898 number, the spy opens clear 52-58602 number, the spy opens clear 52-152302 number, the spy opens clear 54-85802 number, the spy opens clear 60-190392 number, the spy opens clear 58-120531 number, the spy opens clear 63-176187 number, Te Kaiping 1-5889 number, Te Kaiping 1-280590 number, Te Kaiping 1-118489 number, Te Kaiping 1-148592 number, Te Kaiping 1-178496 number, Te Kaiping 1-188315 number, Te Kaiping 1-154797 number, Te Kaiping 2-235794 number, Te Kaiping 3-260100 number, Te Kaiping 3-253600 number, Te Kaiping 4-72079 number, Te Kaiping 4-72098 number, Te Kaiping 3-267400 number, method described in each communique of Te Kaiping 1-141094 number also can be suitable for.In addition, except above-mentioned method, as the manufacture method of electrolytic capacitor and the alternating current of the use particular frequencies that proposes to carry out the method for electrolysis also feasible.For example, United States Patent (USP) the 4th, 276, No. 129 specifications and with the method described in the 4th, 676, No. 878 specifications.

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

In addition, can also use the spy to open clear 52-58602 number, the spy opens clear 52-152302 number, the spy opens clear 53-12738 number, the spy opens clear 53-12739 number, the spy opens clear 53-32821 number, the spy opens clear 53-32822 number, the spy opens clear 53-32833 number, the spy opens clear 53-32824 number, the spy opens clear 53-32825 number, the spy opens clear 54-85802 number, the spy opens clear 55-122896 number, the spy opens clear 55-132884 number, the spy opens clear 48-28123 number, special public clear 51-7081 number, the spy opens clear 52-133838 number, the spy opens clear 52-133840 number, the spy opens clear 52-133844 number, the spy opens clear 52-133845 number, the spy opens clear 53-149135 number, the spy opens described in each communique of clear 54-146234 number.

The aqueous solution that contains nitric acid can be in the aqueous solution of the nitric acid of concentration 1～100g/L, uses according to add at least a back that aluminum nitrate, sodium nitrate, ammonium nitrate etc. have a nitrate compound of nitrate ion from 1g/L to saturated scope.In addition, contain in the aqueous solution of nitric acid the metals that aluminium alloy contained such as all right dissolved iron, copper, manganese, nickel, titanium, magnesium, silicon.

Particularly, in the aqueous solution of nitric acid of concentration of nitric acid 5～15g/L, dissolve aluminum nitrate, and it is more satisfactory that aluminium ion concentration is adjusted into the solution of 3～7g/L.

When aluminium sheet was carried out the processing of electrolysis asperities continuously, aluminium ion concentration in the aqueous slkali rose, the concavo-convex shape change of the aluminium sheet that forms by the nitric acid alternating current electrolysis.Therefore, the management of the composition of nitric acid electrolyte 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 of concentration of nitric acid 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 nitric acid and water so that liquid consists of the control desired value.Then, overflow from circulating tank, keep certain liquid measure by making electrolyte because of adding nitric acid and water and increasing.As the nitric acid that adds, can use the material of 30～70 industrial quality %.

Conductivity meter and densimeter preferably use the meter that passes through temperature-compensating respectively.Densimeter preferably uses differential pressure type.

The sample that the employed electrolyte of forming from liquid of mensuration is taked, use the heat exchanger different with electrolyte be controlled to be uniform temperature (as, 40 ± 0.5 ℃) after, be used further to measure, this method is more satisfactory from the raising aspect consideration of measuring precision.

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

The temperature that contains the aqueous solution of nitric acid, preferred more than 30 ℃, and also preferred below 55 ℃.

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., preferred square wave or trapezoidal wave, preferred especially trapezoidal wave.Trapezoidal wave is meant waveform shown in Figure 2.In this trapezoidal wave, electric current is from 0 time to peaking (TP) preferred 0.5～3msec.When TP surpasses 3msec, particularly use when containing the aqueous solution of nitric acid, be subjected to the influence of the micro constitutent in the electrolyte of the representatives such as ammonium ion that increase by electrolytic treatments naturally-occurring easily, be difficult to carry out uniform graining.Its result, the pollution resistance when becoming lithographic plate may descend.

The duty ratio that can use trapezoidal wave to exchange is 1: 2～2: 1 a power supply.Open described in the flat 5-195300 communique as the spy, aluminium is given in the electric mode without the indirect of conductor cylinder, preferred duty ratio is 1: 1 a power supply.

The frequency that can use trapezoidal wave to exchange is the power supply of 0.1～120Hz.Consider that from equipment 50～70Hz is more satisfactory.When being lower than 50Hz, the carbon electrode of main pole dissolves easily, and when surpassing 70Hz, is subjected to the influence of the inductance composition on the electric power loop easily, and electrical source consumption increases.

Can connect the AC power more than 1 in the electrolytic cell.Control is added in 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 3, impressed current anode is set preferably, makes the part shunting of alternating current.Among Fig. 3,11 is aluminium sheet, and 12 are drum roller (radial drum roller) entad, 13a and 13b are main poles, the 14th, electrolytic treatments liquid, the 15th, electrolyte supply mouth, the 16th, slit, the 17th, electrolyte path, 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 conversion 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, can control current value that participates in the anode reaction that takes place on the aluminium sheet relative and the ratio that participates in the current value of cathode reaction thus with main pole with 2 main electrodes.On the aluminium sheet relative, participate in electricity ratio when anode (electric weight during negative electrode/electric weight) preferred 0.3～0.95 of anode reaction and cathode reaction with main pole.

Electrolytic cell can use the known surface-treated electrolytic cells that are used for such as longitudinal type, platypelloid type, radial mode, and it is desirable especially that the spy opens the radial mode electrolytic cell described in the flat 5-195300 communique.By the electrolyte in the electrolytic cell, with respect to the direct of travel of reel aluminium sheet, can in the same way also can be reverse.

By the nitric acid alternating current electrolysis, can form average opening directly is the pit of 0.5～5 μ m.But, make electric weight more for a long time, cell reaction is more concentrated, also generates the cellular pit that surpasses 5 μ m.

In order to obtain aforesaid Grains, the electric weight summation of the participation anode reaction of the aluminium sheet when cell reaction finishes, preferred 150C/dm ²More than, more preferably 170C/dm ²More than, and preferred 400C/dm ²Below, more preferably 350C/dm ²Below.At this moment current density is represented preferred 20～100A/dm with the peak value of electric current ²

After the processing of nitric acid alternating current electrolysis finished, the most handy pinch roll was removed liquid, after carrying out washing processing 1～10 second, further removed liquid with pinch roll.

Washing is handled and is preferably used playpipe to carry out, and employed playpipe is handled in washing, can for example use, and injection water diffuses into fan-shaped injection sheet has a plurality of playpipes on the width of cloth direction of aluminium sheet.Spray the preferred 20～100mm in interval of sheet, and, per 1 preferred 1～20L/min of liquid measure that sprays sheet.Playpipe preferably uses many.

Before the nitric acid alternating current electrolysis,, in the nitric acid alternating current electrolysis, can not form dark recess so if carry out following preelectrolysis.

Preelectrolysis is the operation of the starting point of the pit formation when forming the nitric acid alternating current electrolysis.Use does not allow to be subject to the influence of aluminium plate matter, and the very strong hydrochloric acid of corrosion resistance, carry out electrolysis a little after, can make the surface be formed uniformly pit as starting point.

In the preelectrolysis, the preferred 1～15g/L of concentration of hydrochloric acid, in addition, the preferred 30～70C/m of the electric weight during anode ²

After the preelectrolysis,, preferably implement caustic corrosion in order to remove crude removal.Preferred 0.2～the 0.6g/m of aluminium meltage in the caustic corrosion ²

＜the second caustic corrosion is handled 〉

The purpose that second caustic corrosion of being carried out between nitric acid alternating current electrolysis and hydrochloric acid alternating current electrolysis is handled is: make the dirt dissolving that in the nitric acid alternating current electrolysis, is generated, and the marginal portion dissolving that makes formed pit in the nitric acid alternating current electrolysis.Second caustic corrosion is handled fundamental sum first caustic corrosion and is handled identically, below difference only is described.

During second caustic corrosion is handled, the preferred 0.05g/m of etching extent ²More than, more preferably 0.1g/m ²More than, and preferred 4g/m ²Below, more preferably 3.5g/m ²Below.Etching extent is very little the time, and in non-image of lithographic plate, the marginal portion of the pit that is generated in the nitric acid alternating current electrolysis can not become smoothly, hangs China ink easily, therefore might the pollution resistance variation.On the other hand, when etching extent was too many, concavo-convex the diminishing that is generated in the nitric acid alternating current electrolysis therefore might anti-seal variation.

During second caustic corrosion is handled, more than the preferred 30g/L of the concentration of aqueous slkali, more preferably more than the 300g/L, and below the preferred 500g/L, more preferably below the 450g/L.

In addition, aqueous slkali preferably contains aluminium ion.More than the preferred 1g/L of aluminium ion concentration, more preferably more than the 50g/L, and below the preferred 200g/L, more preferably below the 150g/L.Aforesaid aqueous slkali, can water and the caustic soda aqueous solution and the sodium aluminate of 48 quality % modulate.

During second caustic corrosion was handled, the temperature of aqueous slkali was preferred more than 30 ℃, more preferably more than 35 ℃, and also preferred below 60 ℃, more preferably below 50 ℃.

During second caustic corrosion was handled, the processing time was preferred more than 1 second, more preferably more than 2 seconds, and also preferred below 30 seconds, more preferably below 10 seconds.

＜the second abatement processes 〉

After carrying out second caustic corrosion processing,, preferably carry out pickling (second abatement processes) in order to remove the dirt of remained on surface.The second abatement processes fundamental sum, first abatement processes is identical, below difference only is described.

In second abatement processes, preferably use nitric acid or sulfuric acid.

In second abatement processes, the preferred use contained the acid of 1～400g/L and the aluminum ions acid solution of 0.5～8g/L.

In second abatement processes, the processing time is preferred more than 1 second, more preferably more than 4 seconds, and also preferred below 60 seconds, more preferably below 20 seconds.

＜hydrochloric acid alternating current electrolysis 〉

The hydrochloric acid alternating current electrolysis is to contain the electrochemical asperities processing that the use in the aqueous solution of hydrochloric acid exchanges.By the hydrochloric acid alternating current electrolysis, can on surface of aluminum plate, form suitable sag and swell.

The hydrochloric acid alternating current electrolysis can be with carrying out with the roughly the same method of above-mentioned nitric acid alternating current electrolysis except the electrolyte difference.Difference below only is described.

Contain aqueous solution of hydrochloric acid, can be in the aqueous solution of hydrochloric acid of concentration 1～100g/L, according to add at least a back use that aluminium chloride, sodium chloride, ammonium chloride etc. have the salt acid compound of chlorion from 1g/L to saturated scope.In addition, contain in the aqueous solution of hydrochloric acid metals that aluminium alloy contained such as all right dissolved iron, copper, manganese, nickel, titanium, magnesium, silicon.

Particularly, in the aqueous solution of nitric acid of concentration of hydrochloric acid 2～10g/L, dissolve aluminium chloride, and it is more satisfactory that aluminium ion concentration is adjusted into the solution of 3～7g/L.

The temperature that contains aqueous solution of hydrochloric acid is preferred more than 25 ℃, more preferably more than 30 ℃, and also preferred below 55 ℃, more preferably below 40 ℃.

Therefore only the aluminium solvability of hydrochloric acid itself is stronger, and electrolysis just can make fine concavo-convex of surface formation a little.This is fine concavo-convex, and average opening directly is 0.01～0.2 μ m, is formed uniformly the whole surface at aluminium sheet.In order to obtain aforesaid Grains, the electric weight summation of the anode reaction of the participation aluminium sheet when cell reaction finishes, preferred 10C/dm ²More than, more preferably 50C/dm ²More than, and preferred 100C/dm ²Below, more preferably 80C/dm ²Below.At this moment current density is represented preferred 20～100A/dm with the peak value of electric current ²

When aluminium sheet was carried out the processing of electrolysis asperities continuously, the aluminium ion concentration in the aqueous slkali rose, by the concaveconvex shape change of the formed aluminium sheet of hydrochloric acid alternating current electrolysis.Therefore, the management of the composition of electrolysis of hydrochloric acid liquid is best carries out according to following method.

When aluminium sheet was carried out the processing of electrolysis asperities continuously, aluminium ion concentration in the aqueous slkali rose, the concavo-convex shape change of the aluminium sheet that forms by the nitric acid alternating current electrolysis.Therefore, the management of the composition of nitric acid electrolyte 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 of concentration of hydrochloric acid 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 hydrochloric acid and water so that liquid consists of the control desired value.Then, overflow from circulating tank, keep certain liquid measure by making electrolyte because of adding hydrochloric acid and water and increasing.As the hydrochloric acid that adds, can use the material of 10～40 industrial quality %.

Conductivity meter and densimeter preferably use the meter that passes through temperature-compensating respectively.Densimeter preferably uses differential pressure type.

To in order to measure that liquid is formed and from the sample that electrolyte is adopted, utilize the heat exchanger different with electrolyte be controlled to be uniform temperature (as, 35 ± 0.5 ℃) after, be used further to measure, this method is more satisfactory from the raising aspect consideration of measuring precision.

＜the three caustic corrosion is handled 〉

The purpose that the 3rd caustic corrosion of being carried out behind the hydrochloric acid alternating current electrolysis is handled is: make the dirt dissolving that generates in the hydrochloric acid alternating current electrolysis, and the marginal portion dissolving that makes formed pit in the hydrochloric acid alternating current electrolysis.The 3rd caustic corrosion is handled fundamental sum first caustic corrosion and is handled identically, below difference only is described.

During the 3rd caustic corrosion is handled, the preferred 0.05g/m of etching extent ²More than, more preferably 0.1g/m ²More than, and preferred 0.3g/m ²Below, more preferably 0.25g/m ²Below.Etching extent is very little the time, and in non-image of lithographic plate, the marginal portion of the pit that generates in the hydrochloric acid alternating current electrolysis can not become smoothly, hangs China ink easily, therefore might the pollution resistance variation.On the other hand, when etching extent was too many, concavo-convex the diminishing that is generated in nitric acid alternating current electrolysis and the hydrochloric acid alternating current electrolysis therefore might anti-seal variation.

During the 3rd caustic corrosion was handled, more than the preferred 30g/L of the concentration of aqueous slkali, in addition, what generated in the hydrochloric acid alternating current electrolysis that makes the last stage concavo-convexly became too small, below the preferred 100g/L, more preferably below the 70g/L.

In addition, aqueous slkali preferably contains aluminium ion.More than the preferred 1g/L of aluminium ion concentration, more preferably more than the 3g/L, and below the preferred 50g/L, more preferably below the 8g/L.Aforesaid aqueous slkali, can water and the caustic soda aqueous solution and the sodium aluminate of 48 quality % modulate.

During the 3rd caustic corrosion was handled, the temperature of aqueous slkali was preferred more than 25 ℃, more preferably more than 30 ℃, and also preferred below 60 ℃, more preferably below 50 ℃.

During the 3rd caustic corrosion was handled, the processing time was preferred more than 1 second, more preferably more than 2 seconds, and also preferred below 30 seconds, more preferably below 10 seconds.

＜the three abatement processes 〉

After carrying out the 3rd caustic corrosion processing,, preferably carry out pickling (the 3rd abatement processes) for the dirt (smut) of removing remained on surface.The 3rd abatement processes fundamental sum first abatement processes is identical, below difference only is described.

In the 3rd abatement processes, use and the anodized of carrying out below in the solution of employed electrolyte (as, sulfuric acid) identical type, can omit the washing step between the 3rd abatement processes and the anodized, thereby more satisfactory.

In the 3rd abatement processes, the preferred use contained the acid of 5～400g/L and the aluminum ions acid solution of 0.5～8g/L.

In the 3rd abatement processes, the processing time is preferred more than 1 second, more preferably more than 4 seconds, and also preferred below 60 seconds, more preferably below 15 seconds.

In the 3rd abatement processes, as abatement processes liquid, use and the anodized of carrying out below in during the solution of employed electrolyte identical type, after abatement processes, can omit the processing and the washing of removing liquid and handle with pinch roll.

＜anodized 〉

To aluminium sheet, also to further implement anodized through above-mentioned processing.Anodized can be carried out with the employed in the past method in this field.For example: at sulfuric acid concentration is 50～300g/L, and aluminum concentration is in the following solution of 5 quality %, is anode with the aluminium sheet, and energising can form anode oxide film.Employed solution in the anodized can be used singly or in combination of two or more thereof following solution: sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, amidosulfonic acid etc.

At this moment, can also 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 listed below: the 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 can contain the concentration of 0～10000ppm.

The condition of anodized is carried out various variations according to the difference of the electrolyte that uses, and can not decide without exception, common concentration of electrolyte 1～80 quality %, 5～70 ℃ of solution temperatures, current density 0.5～60A/dm ², voltage 1～100V, 15 seconds～50 minutes condition of electrolysis time is more suitable, can be adjusted into desired anode oxide film.

In addition, can also use the method described in following each communique: the spy opens clear 54-81133 number, spy and opens clear 57-47894 number, spy and open clear 57-51289 number, spy and open clear 57-51290 number, spy and open clear 57-54300 number, spy and open clear 57-136596 number, spy and open clear 58-107498 number, spy and open clear 60-200256 number, spy and open clear 62-136596 number, spy and open clear 63-176494 number, spy and open flat 4-176897 number, spy and open flat 4-280997 number, spy and open flat 6-207299 number, spy and open flat 5-24377 number, spy and open flat 5-32083 number, spy and open flat 5-125597 number, spy and open flat 5-195291 number.

Wherein, open clear 54-12853 number and spy as the spy and open described in the clear 48-45303 communique,, preferably use sulfuric acid solution as electrolyte.Sulfuric acid concentration in the electrolyte, preferred 10～300g/L (1～30 quality %), more preferably 50～200g/L (5～20 quality %), in addition, aluminium ion concentration, preferred 1～25g/L (0.1～2.5 quality %), more preferably 2～10g/L (0.2～1 quality %).Aforesaid electrolyte can be by for example, adds aluminum sulfate and wait and modulate in sulfuric acid concentration is the dilute sulfuric acid of 50～200g/L.

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

The liquid temperature of electrolyte, preferred 25～55 ℃, more preferably 30～50 ℃.

When carrying out anodized in containing the electrolyte of sulfuric acid, aluminium sheet and to can external dc between the utmost point also can add interchange.

During to the aluminium sheet external dc, 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 " (epithelium than around part of thickening) phenomenon is preferably in the beginning of anodized, with 5～10A/dm ²The low current density impressed 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 in downstream is more than the electric current of dc source of upstream side.Carry out aforesaid electric current and distribute, be not easy to take place the so-called phenomenon of burning, its result, anodized at a high speed becomes possibility.

When carrying out anodized continuously, preferably adopt by electrolyte and carry out for electric mode for the solution of electricity aluminium sheet.

Carry out anodized under aforesaid condition, can obtain having the perforated membrane in a large amount of holes that is known as macropore, usually, its average pore size is 5～50nm, and average hole density is 300～800/μ m ²

Preferred 1～the 5g/m of the amount of anode oxide film ²If be lower than 1g/m ², easily in spite of wound, and surpass 5g/m on the version ²The time, need a large amount of electric power in the manufacturing, uneconomical economically.The amount of anode oxide film, more preferably 1.5～4g/m ²Near the difference of the anode oxide film amount between in addition, the central portion of aluminium sheet and the edge part is with 1g/m ²Below be advisable.

As the employed electrolysis unit of anodized, can use the spy to open clear 48-26638 number, spy and open clear 47-18739 number, special public clear 58-24517 number, spy and open the device described in each communique of 2001-11698 number.

Wherein, device shown in Figure 4 is more suitable.Fig. 4 is a routine skeleton diagram that the surface of aluminium sheet is carried out the device of anodized.

In the anodized device 410 shown in Figure 4, for by electrolyte to aluminium sheet 416 energising, be provided with to electric groove 412 at the upstream side of the direct of travel of aluminium sheet 416, the downstream is provided with anodized groove 414.Aluminium sheet 416 is transported according to the direction shown in the arrow among Fig. 4 by deflector roll (pass roller) 422 and 428.Giving in the electric 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 anode oxide film.

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

Giving between electric groove 412 and the anodized groove 414, as shown in Figure 4, the groove that does not accumulate electrolyte that is known as medial launder 413 is being set preferably.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.Pinch roll 424 preferably is set in the medial launder 413,, by-pass current is reduced to seldom to remove liquid.Electrolyte by pinch roll is removed is discharged to outside the anodized device 410 from leakage fluid dram 442.

In order to reduce the loss of voltage, make the electrolyte 418 that stays to storage in the electric groove 412 than storing up electrolyte 426 high temperature and/or the high concentration of staying in the anodized groove 414.In addition, electrolyte 418 and 426 composition, temperature etc. are by the decisions such as cost of the hardness of the shape of the macropore that forms efficient, anode oxide film of anode oxide film, anode oxide film, voltage, electrolyte.

Give in electric groove 412 and the anodized groove 414,, carry out feeding by giving nozzle for liquid 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, be provided with slit for nozzle for liquid 436 and 438, the liquid with the ejection of making flows structure stable on width.

In anodized groove 414, from anode 430, shield 440 is set across the opposite side of aluminium sheet 416, suppress the opposite side that electric current flows to the anode oxide film one side of wanting to form aluminium sheet 416.Preferred 5～the 30mm in the interval of aluminium sheet 416 and shield 440.Dc source 434 preferably uses a plurality of, connects side of the positive electrode jointly and uses.Thus, can control CURRENT DISTRIBUTION in the anodized groove 414.

In addition, anodized device shown in Figure 5 is connected in series above-mentioned anodized device 2 grooves shown in Figure 4 and forms.

＜sealing of hole is handled 〉

Among the present invention, can also be as required, the sealing of hole that the macropore that exists in the antianode oxide-film seals is handled.Sealing of hole is handled and can be carried out according to known method such as boiled water processing, hot water treatment, steam treatment, sodium metasilicate processing, nitrite treatments, ammonium acetate processing.For example, can open flat 4-4194 communique, spy with the public clear 56-12518 communique of spy, spy opens flat 5-202496 communique, spy and opens described apparatus and method such as flat 5-179482 communique and carry out sealing of hole and handle.

＜hydrophilicity-imparting treatment 〉

After the anodized or after the sealing of hole processing, can carry out hydrophilicity-imparting treatment.As hydrophilicity-imparting treatment, can be listed below: 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 esters 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 44-6409 communique 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 58-16893 communique and described lipophile organic high molecular compound of the clear 58-18291 communique of Te Kai and the formation of divalent metal, 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 59-101651 communique carries out primary coat.

In addition, can also enumerate the processing of carrying out primary coat with following material: the spy opens the described phosphate of clear 62-019494 communique, the spy opens the described soluble epoxide compound of clear 62-033692 communique, the spy opens the described phosphoric acid converted starch of clear 62-097892 communique, the spy opens the diamine compound of putting down in writing in the clear 63-056498 communique, the spy opens the described amino acid whose inorganic or organic acid of clear 63-130391 communique, the spy opens the described organic phospho acid that contains carboxyl or hydroxyl of clear 63-145092 communique, the spy opens the described compound that contains amino and phosphonate group of clear 63-165183 communique, the described specific carboxylic acid derivates of Te Kaiping 2-316290 communique, the described phosphate of Te Kaiping 3-215095 communique, the described compound that has the oxyacid base of 1 amino and 1 phosphorus of Te Kaiping 3-261592 communique, the aliphatic or the aromatic series phosphonic acids of the described phenyl-phosphonic acid of Te Kaiping 5-246171 communique etc., Te Kaiping 1-307745 communique is described to contain the S atomic compound as thiosalicylic acid, Te Kaiping 4-282637 communique is described to have the compound of group of the oxyacid of phosphorus.

Have again, can also open the described acid dyes of clear 60-64352 communique with the spy and carry out painted.

In addition, desirable method of hydrophilizing 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 order described in No. 066 specification and the 3rd, 181, No. 461 specifications of United States Patent (USP) are implemented.

Alkali silicate can list: 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 earth metal salt or 4 families (IVB family) slaine.Alkali earth metal salt is listed below: the nitrate of calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate etc.; Sulfate; Hydrochloride; Phosphate; Acetate; Oxalates; Borate etc.4 families (IVB family) slaine is listed below: titanium tetrachloride, titanium trichloride, titanium potassium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetra iodide, chloride oxidation zirconium, zirconium dioxide, zirconium oxychloride, zirconium chloride.Above-mentioned alkali earth metal salt and 4 families (IVB family) slaine are used singly or two or more kinds in combination.

The Si amount of absorption can be measured by fluorescent x-ray analysis device, the preferred 1.0～15.0mg/m of its adsorbance by the alkali silicate processing ²

Handle by this alkali silicate, can make the effect of support body for lithographic plate printing plate surface acquisition to the dissolubility resistent raising of alkaline-based developer, can suppress the stripping of aluminium component in developer solution, make the reducing of tired caused development gas of developer solution.

Have, the hydrophilicity-imparting treatment of being undertaken by the formation of hydrophilic priming coat can be opened the condition described in clear 59-101651 communique and the clear 60-149491 communique of Te Kai and order is implemented according to the spy again.

The hydrophilic vinyl polymer that this method is used is listed below: polyvinyl sulfonic acid, the p-styrene sulfonic acid etc. that contains sulfo group contain 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 uses of this method can list: contain and be selected from-NH ₂Base ,-compound of at least a group in COOH base and the sulfo group.

＜drying 〉

Obtain according to the method described above after the support body for lithographic plate printing plate, 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 remove liquid with pinch roll after carry out again.

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

Preferred 2～15 seconds of drying time.

(management that liquid is formed)

Among the present invention, the most handy spy of composition of employed various treatment fluids opens the method for putting down in writing in the 2001-121837 communique and manages in the above-mentioned surface treatment.Modulate a plurality of treatment fluid samples of various concentration in advance, measure hyperacoustic spread speed in 2 kinds of liquid temperature respectively, make rectangular tables of data, in the processing, preferably The real time measure liquid temperature and hyperacoustic spread speed are controlled concentration according to it.In abatement processes, when using the electrolyte more than the sulfuric acid concentration 250g/L, preferably carry out the control of concentration especially with said method.

In addition, employed each electrolyte in processing of electrolysis asperities and the anodized is below the preferred 100ppm of Cu concentration.If Cu concentration is too high, in case stop production line, Cu separates out on the aluminium sheet, and when circuit turned round again, the Cu that separates out was transferred on the deflector roll, might become the reason of handling spot.

[original edition of lithographic printing plate]

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

Be applicable to that photosensitive composite of the present invention is listed below: the thermal positive type photosensitive composition (below, said composition and use its image recording layer to be called " thermal positive type ") that contains alkali-soluble macromolecular compound and photo-thermal conversion material, the hot negative photosensitive composition (below be called " hot minus ") that contains hardening compound and photo-thermal conversion material, photo-polymerization type photosensitive composite (below be called " photopolymer type "), the negative photosensitive composition (below be called " common minus ") that contains diazo resin or optical cross-linked resin, the positive light sensitivity composition (below be called " common eurymeric ") that contains benzoquinones diazido compound, the photosensitive composite (below be called " non-processor type ") that does not need special developing procedure.Below above-mentioned good photosensitive composite is illustrated.

＜thermal positive type 〉

＜photosensitive layer 〉

The photosensitive composite of thermal positive type contains alkali-soluble 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-soluble macromolecular compound.

The alkali-soluble macromolecular compound can be enumerated: the resin and the mixture more than 2 kinds thereof that contain acidic groups in the molecule.Particularly, contain phenol hydroxyl, sulfoamido (SO ₂NH-R (in the formula, the R representation hydrocarbyl)), active imido grpup (SO ₂NHCOR ,-SO ₂NH SO ₂R ,-CONH SO ₂R (various in R representation hydrocarbyl)) wait the resin of acidic groups, more satisfactory from dissolubility aspect consideration to alkaline developer.

Especially aspect good by the image forming in the exposure of light such as infrared laser, the resin that contains the phenol hydroxyl is more satisfactory, can be listed below: phenolic resins, metacresol-formaldehyde resin, paracresol-formaldehyde resin ,/to cresols-formaldehyde resin, phenol/cresols (, to and/to mixing any) novolac resin of mixing-formaldehyde resin (phenol-cresols-formaldehyde copolymer resin) etc.

Can also enumerate macromolecular compound, the spy that the spy opens record in the 2001-305722 communique (particularly [0023]～[0042]) in addition and open the macromolecular compound that the macromolecular compound, the spy that contain the represented recurring unit of useful general formula (1) that put down in writing in the 2001-215693 communique open record in the 2002-311570 communique (particularly [0107]).

As photo-thermal conversion material, consider that from the recording sensitivity aspect pigment or the dyestuff of photo-absorption region preferably arranged at the region of ultra-red of wavelength 700～1200nm.As dyestuff, be listed below: azo dyes, metal complex azo dyes, pyrazolone dyestuff, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carboniumion dye, benzoquinone imine dyestuff, methine dyes, anthocyanin dye, fish shark (ス Network ヮ リ リ ゥ system) pigment, pyralium salt, sulfo-slaine ligand (as, sulfo-nickel ligand).Wherein, preferred anthocyanin dye, especially preferred spy opens the represented anthocyanin dye of putting down in writing in the 2001-305722 communique of general formula (1).

In the photosensitive composite of thermal positive type, can contain the dissolving inhibitor.Can enumerate the middle dissolving inhibitor of putting down in writing in [0053]～[0055] that Ru Te opens the 2001-305722 communique as the dissolving inhibitor.

In addition, in the photosensitive composite of thermal positive type, but preferably contain sensitivity conditioning agent, obtain the oven dry agent of video immediately after the heating that is used to expose, as the compounds such as dyestuff of image colouring agent, the surfactant that coating and Treatment Stability are improved as additive.Aforesaid compound, preferred spy opens the material of putting down in writing in [0056]～[0060] of 2001-305722 communique.

Except above-mentioned, it is also more suitable that the spy opens the photosensitive composite of write up in the 2001-305722 communique.

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 enumerate following type: in a side the good bottom of anti-seal 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 the tolerance of developing.The B layer generally contains photo-thermal conversion material.Photo-thermal conversion material can be enumerated aforesaid dyestuff.

Employed resin in the A layer considers that from anti-seal and the good aspect of solvent resistance the monomer that can enumerate to contain sulfoamido, active imido grpup, phenol hydroxyl etc. is the polymer that copolymer composition obtains.Employed resin in the B layer can be enumerated the aqueous alkaline solution-soluble resin that contains the phenol hydroxyl.

In the employed composition,, can also contain various additives as required in A layer and the B layer except described resin.Particularly, it is more suitable that the spy opens the various additives of putting down in writing in 2002-3233769 communique [0062]～[0085].In addition, the above-mentioned spy additive of opening record in [0053]～[0060] of 2001-305722 communique also can be suitable for.

Constitute each composition and the content thereof of A layer and B layer, preferred spy opens the related content of putting down in writing in the flat 11-218914 communique.

＜intermediate layer 〉

The intermediate layer preferably is set between the image recording layer of thermal positive type and the support.The composition that the intermediate layer is contained can be enumerated the various organic compounds that the spy opens [0068] middle record of 2001-305722 communique.

＜other 〉

The manufacture method of the image recording layer of thermal positive type and method for platemaking can use the spy to open the method for putting down in writing in the 2001-305722 communique.

＜hot minus 〉

The photosensitive composite of hot minus contains hardening compound and photo-thermal conversion material.The image recording layer of hot minus is hardened by the infrared laser illuminated portion and forms the photosensitive layer of the minus of image portion.

＜polymer layer 〉

As one type of the image recording layer of hot minus, can enumerate the image recording layer (polymer layer) of aggretion type.Polymer layer contains photo-thermal conversion material, free radical generating agent, as the free-radical polymerised compound and the adhesive polymer of hardening compound.In the polymer 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 sclerosis.

As photo-thermal conversion material, can enumerate as employed photo-thermal conversion material in the above-mentioned thermal positive type.The concrete example of particularly preferred anthocyanin pigment is documented in [0017]～[0019] that the spy opens the 2001-133969 communique.

As free radical generating agent, can enumerate salt.Particularly preferred salt is documented in [0030]～[0033] that the spy opens the 2001-133969 communique.

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

As adhesive polymer, can enumerate the wire organic polymer.The wire organic polymer that for example water or weak base glassware for drinking water is had solubility or swellability.Wherein, side chain has (methyl) acrylic resin of unsaturated group such as aryl, acryloyl group or benzyl and carboxyl, and it is more suitable to consider from the good balanced 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 2001-133969 communique.

In the photosensitive composite of hot minus, preferably contain the additive surfactant of coating (as be used to improve) of record in [0061]～[0068] that the spy opens the 2001-133969 communique.

The manufacture method of polymer layer and method for platemaking can use the spy to open the method for write up in the 2001-133969 communique.

＜sour cross-linked layer 〉

In addition, as the another kind of type of the image recording layer of hot minus, can enumerate the image recording layer (sour cross-linked layer) of sour cross-linking type.The acid cross-linked layer contain photo-thermal conversion material, hot acid propellant, as the hardening compound pass through sour crosslinked compound (crosslinking agent) and in the presence of acid can and the alkali-soluble macromolecular compound that reacts of crosslinking agent.In the acid cross-linked layer, photo-thermal conversion material is transformed into heat with the infrared ray that absorbs, and the hot acid propellant is produced acid by this thermal decomposition, and crosslinking agent and alkali-soluble macromolecular compound react by the acid that produces, and sclerosis.

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

As the hot acid propellant, can enumerate as the heat-decomposing compound of employed acid-producing agent etc. in the phototropic agent of photopolymerisable light trigger, pigment, the microetch etc.

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

As the alkali-soluble macromolecular compound, can enumerate as: novolac resin, side chain contain the polymer of hydroxyaryl.

＜photopolymer type 〉

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

As the addition polymerization compound, can 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, adopt as monomer, prepolymer, their chemical form of mixture etc.The example of monomer has: 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 enumerate urethanes is the addition polymerization compound.

As Photoepolymerizationinitiater initiater, can be according to the wavelength of the light source that uses, select to use various Photoepolymerizationinitiater initiaters aptly or the paralled system (light initiation system) of Photoepolymerizationinitiater initiater more than 2 kinds.For example, the spy opens the initiator system of record in 2001-22079 communique [0021]～[0023].

Polymer binder not only works as the film 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.Aforesaid organic high molecular polymer can exemplify the spy and open the material of putting down in writing in [0036]～[0063] of 2001-22079 communique.

In the photo-polymerization type photosensitive composite of photopolymer type, preferably contain record in [0079]～[0088] that the spy opens the 2001-22079 communique additive (as, be used to improve surfactant, colouring agent, plasticizer, the thermal polymerization terminator of coating).

In addition, on the image recording layer of photopolymer type,, oxygen barrier property protective layer is set preferably in order to prevent the polymerization termination of oxygen.The polymer that contains in the oxygen barrier property protective layer can be enumerated as polyvinyl alcohol, its copolymer.

Have again, preferably be provided with as special intermediate layer or the adhesive layer of putting down in writing in [0124]～[0165] of 2001-228608 communique of opening.

＜common minus 〉

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

Diazo resin is listed below: aromatic series diazol and formaldehyde etc. contain the condensation product of the compound formation of active carbonyl group; The reaction product that the condensation product of p-benzene diazonium amine and formaldehyde and hexafluorophosphate or tetrafluoroborate form, i.e. organic solvent solubility diazo resin inorganic salts.Particularly, it is more satisfactory that the spy opens the HMW diazonium compound of putting down in writing in the clear 59-78340 communique that contains more than the above 6 amount bodies of 20mol%.

As adhesive, can enumerate with acrylic acid, methacrylate, crotonic acid or maleic acid is the copolymer of necessary composition.Object lesson is as follows: open the multiple copolymer that monomers such as 2-ethoxy (methyl) acrylate put down in writing in the clear 50-118802 communique, (methyl) acrylonitrile, (methyl) acrylic acid form as the spy, open alkyl acrylate, (methyl) acrylonitrile and the formed multiple copolymer of putting down in writing in the clear 56-4144 communique of unsaturated carboxylic acid as the spy.

In the photosensitive composite of common minus, preferably contain as the spy of additive open record in [0014]～[0015] of flat 7-281425 communique compounds such as oven dry agent, dyestuff, the plasticizer that is used to pay soft film coating and abrasion performance, development accelerant, be used to improve the surfactant of coating.

Below the photosensitive layer of common minus, the spy preferably is set opens the intermediate layer of putting down in writing in the 2000-105462 communique 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 benzoquinones diazido compound.Wherein, can enumerate the photosensitive composite that contains o-benzoquinones diazido compound and alkali-soluble macromolecular compound.

As o-benzoquinones diazido compound, be listed below: 1, ester, United States Patent (USP) the 3rd that 2-naphthoquinones-2-diazido-5-sulfonic acid chloride and phenolic resins or cresol-formaldehyde resin form, 635, put down in writing in No. 709 specifications 1, the ester that 2-naphthoquinones-2-diazido-5-sulfonic acid chloride and 1,2,3,-thrihydroxy-benzene acetone resin form.

As the alkali-soluble macromolecular compound, be listed below: copolymer, the spy of phenolic resins, cresol-formaldehyde resin, phenol-cresols-formaldehyde copolymer resins, polycarboxylated styrene, N-(4-hydroxy phenyl) Methacrylamide opens the polymer that contains carboxyl, the spy that put down in writing in the flat 7-36184 communique and opens the acrylic resin that contains the phenol hydroxyl, the spy that put down in writing in the clear 51-34711 communique to open the acrylic resin that contains sulfoamido, the urethane put down in writing in the flat 2-866 communique be resin.

In the photosensitive composite of common eurymeric, preferably contain surfactant that is used to improve coating of record in [0031] that compound, the He Te such as sensitivity conditioning agent, oven dry agent, dyestuff that open record in [0024]～[0027] of flat 7-92660 communique as the spy of additive open flat 7-92660 communique.

Below the photosensitive layer of common eurymeric, preferably be provided with and be applicable to the same intermediate layer, intermediate layer of above-mentioned common minus.

＜non-processor type 〉

The photosensitive composite of non-processor type can list: thermoplasticity particulate polymer-type, microcapsule-type, sulfonic acid generation polymer contain type.They all are the sensible heat 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 particulate polymer-type is that the particulate polymer dispersed of hydrophobicity and hot melt property is in the hydrophilic macromolecule matrix and form.In the image recording layer of thermoplasticity particulate polymer-type, the heat fusion that hydrophobic particulate polymer is produced because of exposure, fusion mutually forms water repellent region, i.e. image portion.

As the particulate polymer, the fusion that obtains by heat fusing between the particulate preferably, the surface is a hydrophily, and the material that might be distributed in the hydrophilic composition such as damping water is desirable more.Concrete example as: Research Disclosure No.33303 (in January, 1992), spy open flat 9-123387 number, with 9-131850 number, with 9-171249 number and the thermoplasticity particulate polymer that discloses record in the 931st, No. 647 specification etc. with 9-171250 number each communique, european patent application.Wherein, preferred polystyrene and polymethyl methacrylate.The particulate polymer on possess hydrophilic property surface can exemplify: polymer itself is hydrophilic material; Make the hydrophilic compounds of polyvinyl alcohol, polyethylene glycol etc. be adsorbed on the particulate polymer surfaces, make the material of surface hydrophilic.

The particulate polymer preferably contains reactive functional group.

As the photosensitive composite of microcapsule-type, can enumerate: the spy opens the material, the spy that put down in writing in the 2000-118160 communique and opens the microcapsule-type of putting down in writing in the 2001-277740 communique that comprises the compound with heat reactivity functional group.

Sulfonic acid generation polymer contains the sulfonic acid generation polymer that uses in the photosensitive composite of type, can enumerate: the spy opens the polymer that has sulfonate group, disulfonic acid base or sec-or tert-sulfoamido on the side chain of putting down in writing in the flat 10-282672 communique.

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 the material, the hydrophilic collosol and gel transformation series binding resin that contain hydrophilic groups such as hydroxyl, carboxyl, ethoxy, hydroxypropyl, amino, amino-ethyl, aminopropyl, carboxymethyl.

The image recording layer layer of non-processor type does not need special developing procedure, just 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 putting down in writing in the 2002-178655 communique.

＜back coating 〉

The back side of the lithographic printing original of the present invention that on resulting support body for lithographic plate printing plate, various image recording layers is set as described above and obtains according to the present invention, in order to prevent the scratch of image recording layer when overlapping, the cover layer that organic high molecular compound constitutes can be set as required.

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

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

Be used for the light source of the active ray of image exposure, be listed below: mercury vapor lamp, metal halide lamp, xenon lamp, chemical lamp.Laser can be enumerated: helium-neon laser (He-Ne laser), argon laser, krypton laser, He-Cd laser, KrF excimer laser, semiconductor laser, YAG laser, YAG-SHG laser.

After the described exposure, image recording layer is under any situation in thermal positive type, hot minus, common minus, common eurymeric and the photopolymer type, and the most handy developer solution develops after the exposure, obtains 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.The method of using the developer solution do not contain alkali silicate in fact to develop can use the spy to open the method for write up in the flat 11-109637 communique.

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

[embodiment]

Specify the present invention with embodiment below, but the present invention is not subjected to the restriction of embodiment.

1-1. the making of support body for lithographic plate printing plate

(embodiment 1～23 and comparative example 1)

With the aluminium alloy modulation motlten metal of forming (remainder is aluminium and inevitable impurity) shown in the table 1, carried out after motlten metal handles and filter, make the ingot bar of thick 500mm, wide 1200mm with the DC casting.After the thickness of flush cut machine with the about 10mm of surface cut, at 550 ℃, keep about 5 hours of soaking, when temperature drops to 400 ℃, make the calendering plate of thick 2.7mm with the hot calender machine.Then with the continuous annealing machine 500 ℃ heat-treat after, prolong by colding pressing, be configured as thick 0.3mm, wide 1060mm, obtain aluminium sheet.

The making of＜calendering cylinder 〉

To consisting of C:1.52 quality %, Si:0.31 quality %, Mn:0.41 quality %, P:0.028 quality %, S:0.002 quality %, Cr:11.6 quality %, Mo:1.05 quality %, Cu:0.12 quality %, V:0.27 quality %, remainder: the SKD11 steel of iron and inevitable impurity is implemented Quenching Treatment and temper, make its hardness Hs become 82, this is had surface roughness Ra is that the cylinder surface of the smooth surface of 0.1 μ m carries out air-jet method 2 times, implements the asperities processing.In the air-jet method, as sand material, and be 90 ° according to angle and spray described sand material with jet face with the aluminium oxide particles of average grain diameter 90 μ m.

Then, with pouncing paper abrasive roller surface up to the deviation of the height of cylinder surface protuberance in 1 μ m.

Afterwards, implement hard chrome plating so that thickness becomes 8 μ m, obtaining Ra is the calendering cylinder of 0.65 μ m.

Finally colding pressing in the manufacturing process of aluminium calendering plate prolonged in the operation, uses the calendering cylinder of making according to the method described above, and it is concavo-convex by calendering (transfer printing) aluminium sheet to be formed.Surface roughness after the calendering is following value.Ra=0.5 μ m, Rmax=3.0 μ m, Sm=100 μ m, Δ a=3.5 μ m, assay method is as described below.

(1) mean roughness

Carrying out the mensuration of two-dimentional roughness with contact pin type fineness gauge (sufcom575, the accurate society in Tokyo system), measure the arithmetic average roughness of 5 ISO4287 defineds, is mean roughness with its mean value.Similarly measure the maximum height Rmax (Ry) of datum length, concavo-convex equispaced (mean value in the datum length) Sm, mean pitch Δ a.

＜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.

Below, carry out following processing with this aluminium sheet.

(1) corrosion treatment in the aqueous alkali

The aqueous solution that will contain NaOH 27wt%, aluminium ion 6.5wt% sprays with playpipe at 60 ℃, and aluminium sheet is carried out corrosion treatment.In the operation of back, be 1.5g/m by the meltage of the aluminium sheet of the one side of electrochemistry asperities processing ²Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.

(2) abatement processes in the acidic aqueous solution

Then, carry out abatement processes.

The waste liquid of employed nitric acid in the electrochemistry asperitiesization of use subsequent processing.Its solution temperature is 35 ℃.Spray decontaminating liquid with injector, carry out 5 second abatement processes.Afterwards, remove liquid with pinch roll.

(3) the electrochemical asperities processing in the aqueous solution of nitric acid

The electrolyte that uses is 35 ℃ of liquid temperature, adds aluminum nitrate in the aqueous solution of concentration of nitric acid 10g/l, and aluminium ion concentration is adjusted to 4.5g/l forms.

Use the power supply that produces alternating current shown in Figure 2, carry out electrochemical asperities processing.The frequency of its alternating current is 60Hz, and electric current is 1.2msec from the 0 time T p that reaches peak value.The duty ratio (ta/T) that exchanges is 0.5.

Current density when the peak value that exchanges during the anode reaction of aluminium sheet is 60A/dm ²The ratio of the electric weight summation when electric weight summation the during anode reaction of aluminium sheet and cathode reaction is 0.95.Be applied to the electric weight on the aluminium sheet, the summation of the electric weight during with the anode reaction of aluminium sheet represents it is 195C/dm ²

The electrolytic treatments groove uses 2 radial mode grooves shown in Figure 3.

The mean value of the relative velocity of aluminium sheet and electrolyte in electrolytic cell is 1.5m/sec (1～2m/sec).Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.

(4) corrosion treatment in the aqueous alkali

The aqueous solution that will contain NaOH 27wt%, aluminium ion 5.5wt% sprays with playpipe at 65 ℃, handles for 8 seconds, and aluminium sheet is carried out corrosion treatment.In the operation of back, be 3g/m by the meltage of the aluminium sheet on the one side of electrochemistry asperities processing ²Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.

(5) abatement processes in the acidic aqueous solution

Then, carry out abatement processes.

Use the waste liquid (dissolved aluminum ion 1.5g/l in the sulfuric acid 300g/l aqueous solution) that produces in the anodized operation described later, under 35 ℃ of solution temperatures, carry out 10 second abatement processes.Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.

＜6〉the electrochemistry asperities processing in the aqueous hydrochloric acid solution

The electrolyte that uses is 35 ℃ of solution temperatures, adds aluminium chloride in the aqueous solution of concentration of hydrochloric acid 5g/l, and aluminium ion concentration is adjusted to 5g/l forms.

Use the power supply of generation trapezoidal wave alternating current shown in Figure 2, carry out electrochemical asperities processing.The frequency of its alternating current is 60Hz, and electric current is 0.8msec from the 0 time T p that reaches peak value.The duty ratio (ta/T) that exchanges is 0.5.

Current density when the peak value that exchanges during the anode reaction of aluminium sheet is 50A/dm ²The ratio of the electric weight summation of the electric weight summation the during anode reaction of aluminium sheet during with cathode reaction is 0.95.Be applied to the electric weight on the aluminium sheet, the summation of the electric weight during with the anode reaction of aluminium sheet represents it is 63C/dm ²

The electrolytic treatments groove uses 1 radial mode groove shown in Figure 3.

The mean value of the relative velocity of aluminium sheet and electrolyte in electrolytic cell is 1.5m/sec.Afterwards, remove liquid with pinch roll, washing, further pinch roll is removed liquid.

＜7〉corrosion treatment in the alkaline aqueous solution

The aqueous solution that will contain NaOH 5wt%, aluminium ion 0.5wt% sprays with playpipe at 35 ℃, makes aluminium sheet dissolving 0.1g/m ², carry out corrosion treatment.Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.

(8) abatement processes in the acid solution

Then, carry out abatement processes.The acidic aqueous solution that uses in the abatement processes is the waste liquid (dissolved aluminum ion 1.5g/l in the sulfuric acid 300g/l aqueous solution) that produces in the anodized of subsequent processing, under 60 ℃ of solution temperatures, carry out 5 second abatement processes.Afterwards, remove liquid with pinch roll.

(9) anodized

Then, this plate is carried out anodized with following condition.

Use is added aluminum sulfate in sulfuric acid 170g/l, and to make aluminium ion concentration be 33 ℃ the electrolyte of 5g/l, and the average current density of the current density that aluminium sheet applied in the electrolytic treatments groove during with the anode reaction of aluminium sheet represented it is 10A/dm ²Condition under, 2.4g/m is set ²The dc anodizing tunicle.Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.

(10) hydrophilicity-imparting treatment

In containing 20 ℃ of aqueous solution of sodium metasilicate 2.5%, flood and carry out hydrophilicity-imparting treatment 10 seconds.Afterwards, remove liquid with pinch roll, washing is further removed liquid with pinch roll.Measure the Si amount on the surface of this aluminium sheet with fluorescent x-ray analysis device.The Si amount on the surface of aluminium sheet is 3.5mg/m ²

Afterwards, blow 90 ℃ 10 seconds of wind, carry out drying.

(embodiment 24～26)

Similarly obtain aluminium sheet with the aluminium alloy and the embodiment 1～23 that form shown in the table 1.Just, the Yanzhong of colding pressing replaces 2 air-jet methods, carry out 2 times with steel grit of average grain diameter 200 μ m shot peening method as sand material, in addition, with obtaining being different from the calendering cylinder of embodiment 1～23 with the same method of the making of above-mentioned calendering cylinder, use this calendering cylinder,, and form concavo-convex on the surface by the transfer printing relief pattern.The surface roughness Ra of aluminium sheet is 0.45 μ m.Obtain support body for lithographic plate printing plate by the following method with this aluminium sheet.

＜surface treatment 〉

Surface treatment is in above-mentioned＜1 〉～＜10 processing in, except the following place of putting down in writing and embodiment 1～23＜1～＜10 surface treatment similarly carry out.

＜1〉corrosion treatment in the alkaline aqueous solution

Except making caustic soda concentration is 370g/L, the aluminum particulate concentration 100g/L, carries out corrosion treatment same as described abovely.The etching extent of the one side that is implemented the described electrochemical asperities processing in back of aluminium sheet, as shown in table 3.

Afterwards, remove liquid, after implementing washing described later and handling, further remove liquid with pinch roll with pinch roll.Washing is handled, and is to use the device of washing processing by the liquid film that freely falls the curtain shape to carry out, and makes the playpipe of the structure that 30 nozzles form a line at interval according to 50mm wash for 5 seconds with having then.

＜2〉abatement processes

Carry out the processing same with embodiment 1～23.Afterwards, remove liquid without pinch roll, carry attached to the state on the aluminium sheet with aqueous solution of nitric acid, time of delivery was 25 seconds.

＜3〉the electrochemical asperities processing of the interchange of the use in the aqueous solution of nitric acid

The summation of the electric weight of electric weight during with the anode reaction of aluminium sheet is represented, is 200C/dm ², in addition, carry out same processing.

＜4〉corrosion treatment in the alkaline aqueous solution

By the aqueous solution 7 seconds of playpipe, carry out corrosion treatment to 64 ℃ of aluminium sheet spraying caustic soda concentration 370g/L, aluminium ion concentration 100g/L, temperature.The etching extent that is implemented electrochemical asperities processing one side of aluminium sheet is 3g/m ²

Afterwards, remove liquid, after implementing washing described later and handling, further remove liquid with pinch roll with pinch roll.Washing is handled, and is to use the device of washing processing by the liquid film that freely falls the curtain shape to carry out, and uses the playpipe of the same structure that uses in handling with the washing of above-mentioned (1) to wash for 5 seconds then.

＜5〉abatement processes

Aluminum nitrate is dissolved in the 300g/L aqueous solution of nitric acid and makes aluminium ion concentration is the aqueous solution (35 ℃ of solution temperatures) of 2g/L, sprays for 10 seconds through playpipe, carries out abatement processes.

Afterwards, remove liquid, after the playpipe of the same structure of employed playpipe was washed processing during the washing of usefulness and above-mentioned (1) was handled, further remove liquid with pinch roll with pinch roll.

＜6〉the electrochemical asperities processing of the interchange of the use in the aqueous hydrochloric acid solution

Carry out the processing same with embodiment 1～23.

＜7〉corrosion treatment in the alkaline aqueous solution

Carry out the processing same with embodiment 1～23.

Afterwards, remove liquid, after implementing washing described later and handling, further remove liquid with pinch roll with pinch roll.Washing is handled, and is to use the device of washing processing by the liquid film that freely falls the curtain shape to carry out, and the playpipe that has Φ 3mm hole at interval in order to 20mm washed for 5 seconds then.

＜8〉abatement processes

By 5 seconds of the aqueous solution (35 ℃ of solution temperatures) of playpipe spraying sulfuric acid concentration 170g/L, aluminium ion concentration 5g/L, carry out abatement processes.The aqueous solution uses the waste liquid of aftermentioned (9) anodized operation.

Afterwards, remove liquid, do not wash processing with pinch roll.

＜9〉anodized

Use anodized device shown in Figure 5 to carry out anodized.

Use aluminum sulfate to be dissolved in the 170g/L aqueous sulfuric acid and make the electrolyte (temperature 33 ℃) of aluminium ion concentration as 5g/L.Anodized proceeds to the average current density of aluminium sheet during anode reaction and becomes 15A/dm ², final oxide-film amount is 2.4g/m ²

Anodized device shown in Figure 5,2 grooves of above-mentioned anodized device shown in Figure 4 are connected in series to be formed.But the 1st groove is different with the dc source number in the 2nd groove.In the anodized device, the electric current summation of the dc source A～H of the 1st groove and the dc source I～L of the 2nd groove is 31,000A, and its electric current distribution and decomposition voltage are as shown in table 2.All the same long with the electrode that each dc source connects.During the anodized, the time that aluminium sheet participates in anode reaction was total up to for 16 seconds.

Afterwards, remove liquid, after the playpipe of the same structure of employed playpipe was washed processing during the washing of usefulness and above-mentioned (1) was handled, remove liquid with pinch roll with pinch roll.

Table 2

＜10〉hydrophilicity-imparting treatment

Make aluminium sheet (20 ℃ of solution temperatures) in the aqueous solution of sodium metasilicate 2.5 quality % flood for 10 seconds.The Si amount of the surface of aluminum plate of measuring with the fluorescent x-ray analysis equipment is 3.5mg/m ²

Afterwards, remove liquid with pinch roll, with and after the playpipe that uses in handling of the washing of above-mentioned (1) playpipe of constructing equally washes processing, further remove liquid with pinch roll.

Blow 90 ℃ 10 seconds of wind then, carry out drying, obtain support body for lithographic plate printing plate.

1-2. the observation on the surface of support body for lithographic plate printing plate

With scanning electron microscope (JSM-5500, society of NEC system, below identical) under 50000 times of multiplication factors, observe on the surface of above-mentioned resulting each support body for lithographic plate printing plate, found that evenly and generated densely the fine concavo-convex of average opening footpath 0.1 μ m.

In addition, under 2000 times of multiplication factors, observe, found that on the surface of the support body for lithographic plate printing plate of embodiment 1～26, evenly to have generated the concavo-convex of average opening footpath 1～5 μ m with scanning electron microscope.And in the support body for lithographic plate printing plate of comparative example 1, concavo-convex inhomogeneous.

In addition, average opening footpath 0.1 μ m fine concavo-convex is to overlap concavo-convex the going up of average opening footpath 1～5 μ m and form.

Have, with the surface of visualization resulting each support body for lithographic plate printing plate, the result does not have streak and face of fine quality good again.

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

On above-mentioned resulting each support body for lithographic plate printing plate, according to the following stated the image recording layer of thermal positive type is set, obtain 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 15 seconds of drying, 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

[changing 1]

In addition, modulating the heat sensing layer coating fluid of following composition, be provided with on the support body for lithographic plate printing plate of priming coat, is 1.8g/m according to the dried coating weight of this heat sensing layer coating fluid (heat sensing layer coating weight) ²Be coated with, dry then, form heat sensing layer (image recording layer of thermal positive type), obtain original edition of lithographic printing plate.

＜heat sensing 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 is than 35/35/30) 0.10g

The cyanine dyestuff A 0.1g that following structural formula is represented

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-hydroxy-beta-naphthalene sulfonic acids

Fluorine is surfactant (メ ガ Off ァ ッ Network F-780F, big Japanese ink chemical industry society system, solid constituent 30 quality %) 0.0045g (solid constituent conversion)

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

Methyl ethyl ketone 12g

[changing 2]

1-4. the evaluation of original edition of lithographic printing plate

The anti-seal and the pollution resistance of lithographic plate are estimated in accordance with the following methods.

(1) anti-seal

Under the condition of drum rotation speed 150rpm, radiation (beam) intensity 10W, the original edition of lithographic printing plate that obtains is carried out describing of image with the Trend Setter of Creo society system.

Afterwards, the PS プ ロ セ ッ サ-940H with the Fujiphoto (strain) of the alkaline developer that following composition is housed is made develops under 30 ℃ of fluid temperatures of maintenance, 20 seconds condition of developing time, obtains lithographic plate.And 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 1,000) 0.5 quality %

Water 96.15 quality %

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

The result is as shown in table 3.The implication of the mark in the table 3 is as described below.

A: the printing number is more than 30000

A-B: the printing number is more than 10000 pieces and is lower than 30000

B: the printing number is lower than 10,000

(2) pollution resistance

The lithographic plate that the evaluation occasion of use and anti-seal obtains with quadrat method, with the ダ ィ ャ of Mitsubishi type F2 printing machine (Mitsubishi Heavy Industries Ltd industry society system), and the red printing ink of DIC-GEOS (s) prints, and prints the pollution condition of the blanket (blanket) after 10,000 with visual valuation.

The result is as shown in table 3.The implication of the mark in the table 3 is as described below.

A: pollution-free

A-B: almost pollution-free

B: pollute in allowed band

C: obviously pollute

Can know from table 3, use the lithographic plate of the support body for lithographic plate printing plate that the manufacture method (embodiment 1～26) by support body for lithographic plate printing plate of the present invention obtains, all have good anti-seal and pollution resistance.

Table 3

In addition, use the lithographic plate of resulting support body for lithographic plate printing plate in embodiment 1～26 to compare the easier adjustment of amount of the damping water on the printing machine at the lithographic plate of comparative example 1 resulting support body for lithographic plate printing plate with use.

Claims (10)

1, a kind of manufacture method of support body for lithographic plate printing plate, it is characterized in that, forming from the teeth outwards by the transfer printing relief pattern on concavo-convex aluminium sheet concavo-convex, the pit of the pit of further overlapping average opening footpath 0.5～5 μ m and average opening footpath 0.05～0.3 μ m carries out anodized then or carries out anodized and hydrophilicity-imparting treatment.

2, the manufacture method of support body for lithographic plate printing plate according to claim 1 is characterized in that, uses and has formed concavo-convex aluminium sheet from the teeth outwards by the transfer printing relief pattern, carries out following processing successively:

(1) carry out electrochemical asperities processing in the aqueous solution of nitric acid,

(2) carry out electrochemical asperities processing in the aqueous hydrochloric acid solution,

(3) anodized.

3, the manufacture method of support body for lithographic plate printing plate according to claim 1 is characterized in that, uses and has formed concavo-convex aluminium sheet from the teeth outwards by the transfer printing relief pattern, carries out following processing successively:

(1) carry out chemical attack in the alkaline aqueous solution and handle,

(2) carry out abatement processes in the acidic aqueous solution,

(3) carry out electrochemical asperities processing in the aqueous solution of nitric acid,

(4) carry out chemical corrosion treatment in the alkaline aqueous solution,

(5) carry out abatement processes in the acidic aqueous solution,

(6) carry out electrochemical asperities processing in the aqueous hydrochloric acid solution,

(7) carry out chemical corrosion treatment in the alkaline aqueous solution,

(8) carry out abatement processes in the acidic aqueous solution,

(9) anodized.

4, according to the manufacture method of each described support body for lithographic plate printing plate in the claim 1～3, wherein said formed concavo-convex aluminium sheet on the surface be the aluminium sheet that contains 0.020～0.2 quality %Cu.

5, according to the manufacture method of each described support body for lithographic plate printing plate in the claim 1～3, the transfer printing of wherein said relief pattern is to carry out in the final calendering procedure of aluminium sheet manufacturing process.

6. the manufacture method of support body for lithographic plate printing plate according to claim 4, the transfer printing of wherein said relief pattern is to carry out in the final calendering procedure of aluminium sheet manufacturing process.

7, according to the manufacture method of each described support body for lithographic plate printing plate in the claim 1～3,6, after the wherein said anodized, further carry out hydrophilicity-imparting treatment.

8. the manufacture method of support body for lithographic plate printing plate according to claim 4 after the wherein said anodized, is further carried out hydrophilicity-imparting treatment.

9. the manufacture method of support body for lithographic plate printing plate according to claim 5 after the wherein said anodized, is further carried out hydrophilicity-imparting treatment.

10, a kind of original edition of lithographic printing plate on the resulting support of each manufacture method in the claim 1～9, further has image recording layer.

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