CN1182979C

CN1182979C - Method for producing support body of offset press plate

Info

Publication number: CN1182979C
Application number: CNB021078750A
Authority: CN
Inventors: 松浦睦; 男; 上杉彰男
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2001-03-27
Filing date: 2002-03-25
Publication date: 2005-01-05
Anticipated expiration: 2022-03-25
Also published as: CN1377785A

Abstract

Disclosed is a method for manufacturing a supporting body for a planographic printing plate which is characterized in that the method for manufacturing a supporting body for a planographic printing plate comprising a surface roughening treatment process and an anodizing treatment process. The surface roughening treatment process comprises an electrolytic surface roughening treatment process and the alkali etching treatment process. In the electrolytic surface roughening treatment process, the anode aggregate capacitance in the electrolytic surface roughening treatment is made to be 50-800 C/dm<2>. In the anodizing treatment for the anodizing treatment process, electrolytic solution containing sulfuric acid is used with the temperature, the conductive rate, and the specific gravity, of the electrolytic solution being controlled to be within certain limits.

Description

The manufacture method of support body for lithographic plate printing plate

Technical field

The present invention relates to the manufacture method of support body for lithographic plate printing plate.

Background technology

As the support of lithographic plate, the past is extensive use of aluminum support.With photosensitive layer adherence is arranged to requiring on the aluminum support, and the performance that when being used to print, keeps soaking water.In order to reach this purpose, to carry out roughening and anodized on the surface of aluminum support usually.If adherence too a little less than, the anti-brush when then printing is just poor, and if adherence when undue strong when video picture, partly remains on the support easily for the non-portrait that should remove, reduced stain resistance.And if can not keep soaking water, printing ink owing to non-portrait part will take place to be obstructed and to pollute the low inferior problem of performance.Thereby to just being necessary to make the technology of certain surface galley that handle, stable performance on the width of aluminum support with support.

Therefore, for foregoing performance is provided, generally to carry out roughening processing and anodized etc. to the surface of support.

Method as the aluminium sheet roughening has methods such as mechanical sandblast and electrochemistry sandblast, it is carried out suitable combination carry out roughening.As mechanical sand-blast, ball milling material method, wire abrasive material method, brushing emery wheel method and hydro-abrasion method etc. are arranged.And, generally adopt the alternating current electrolysis etch as the method for electrochemistry sandblast, and use common simple sinusoidal alternating current or square wave and special alternative current etc. as Faradaic current.And, also can carry out corrosion treatment to aluminium sheet with caustic soda etc. as the pre-treatment of this electrochemistry sandblast.

The mode of electrochemistry sandblast is suitable for continuous processing, and as the method for roughening, using day by day in recent years increases.But when such aluminium sheet was carried out the electrochemistry sandblast, can form with aluminium hydroxide on the surface of aluminium sheet was the powdery layer of main component.

In US Patent specification the 4th, 548, the high-frequency ac electrolysis electric current of having narrated with 140～400Hz on No. 683 just is not easy to generate this powdery layer, forms uniform indenture.Unless such special circumstances are carried out the electrochemistry sandblast and all can be generated powdery layer on surface of aluminum plate.In addition, pass through the aluminium sheet of electrochemistry sandblast like this, carry out anodized, also must carry out silicate in case of necessity handles, coating photosensitive material (comprising the sensible heat material), finish the light sensitive plate master after dry, but the surface of aluminum plate after the electrochemistry sandblast residual powdery layer, sneaked into anodic oxide coating, produce epithelium defective etc., reduced printing performance.

And in special permission communique clear 56-11316 number, disclose the powdery layer that will on the aluminium surface, generate to contact with the sulfuric acid solution that fluid temperature is adjusted to 15～60wt% of 50～90 ℃, the method for removing powdery layer for feature is removed in its dissolving.And on No. the 2577594th, special permission communique, disclose the powdery layer that will on the aluminium surface, produce earlier and be dissolved in the pH value more than 10 by the electrolysis roughening, temperature is 25～60 ℃ a aqueous slkali, being that 50～400g/L, temperature are in 25～65 ℃ the solution based on sulfuric acid in concentration then, is 0.03～0.20g/m at the meltage of aluminium base ²Situation under dissolve, to remove the method for powdery layer.The former method, owing to do not use aqueous slkali simultaneously, shortcoming such as the removal of powdery layer is abundant inadequately, the shape unevenness that is produced by the electrolysis roughening also remains on the surface of aluminium, shortcomings such as the adherence of photosensitive layer and aluminium sheet can reduce in addition, and the pollutant performance of printing is also not enough.And the latter is owing to can remove the powdery layer that produces effectively by enough aqueous slkalis when the electrolysis roughening, but can not remove the unwanted intermetallic compound that is present in surface of aluminum plate, as shown in example in front, in the scope of the composition of strictly not controlling aluminium alloy, it is the place of problem that too serious pollution tolerance worsens.The temperature of aqueous slkali is lower temperature range for 25～60 ℃, and the time all spends on the dissolution process, and this is disadvantageous aspect formation efficiency.

Summary of the invention

Therefore, purpose of the present invention just provides a kind of manufacture method of lithographic printing plate, compares with the lithographic printing plate manufacture method in past, and this support has excellent anti-brush and resistant water-based.

The invention provides the manufacture method of support body for lithographic plate printing plate, it is characterized in that, this method is the manufacture method that has comprised the support body for lithographic plate printing plate of operations such as roughening treatment process and anodized,

Aforesaid roughening treatment process comprises electrolysis roughening operation and caustic corrosion treatment process;

In above-mentioned electrolysis roughening operation, the total electric weight of anode that the electrolysis roughening is handled is 50～800C/dm ²

In above-mentioned anodized operation, the electrolyte that the anodized of supplying with is used contains sulfuric acid, respectively the temperature of electrolyte is controlled at 5～70 ℃ scope, the electrical conductivity of electrolyte is controlled at the scope of 0.1～0.9S/cm, the specific gravity control of electrolyte in 1.05～1.20 scope.

If necessary, operations such as mechanically roughened processing also to suitably be set.

Description of drawings

Fig. 1 is the skeleton diagram that has shown an example of the device that can be used in mechanically roughened processing;

Fig. 2 is the skeleton diagram that has shown an example of the device that can be used in the caustic corrosion processing;

Fig. 3 is the skeleton diagram that has shown an example of the device that can be used in the processing of electrolysis roughening;

Fig. 4 is the skeleton diagram that has shown an example of the device that can be used in anodized;

Fig. 5 is the skeleton diagram that has shown an example of the device that can be used in the sealing of hole processing;

Fig. 6 is the skeleton diagram that has shown an example of the device of coating coating fluid on aluminium alloy plate;

Fig. 7 has shown that the aluminium alloy plate that will be coated with coating fluid carries out the skeleton diagram of an example of dry device;

The specific embodiment

The raw material of support body for lithographic plate printing plate

As support body for lithographic plate printing plate, generally use the aluminium sheet of the surface rational faculty, processability, excellent corrosion resistance of light weight or aluminium alloy plate (below be called " aluminium alloy plate ").As the material for this purpose aluminium alloy plate, being fit to use JIS A 1050 aluminiums, JIS A 1100 aluminiums, JIS A 1070 aluminiums, the Al-Mn of following explanation is that alloy, Al-Mn-Mg are that alloy, Al-Zr are that alloy, Al-Mg-Si are alloy etc.

Relate to JIS A 1050 aluminiums, what be fit to use is to open clear 59-153861 communique the spy, the spy opens clear 61-51395 communique, the spy opens clear 62-146694 communique, the spy opens clear 60-215725 communique, the spy opens clear 60-215726 communique, the spy opens clear 60-215727 communique, the spy opens clear 60-216728 communique, the spy opens clear 61-272367 communique, the spy opens clear 58-11759 communique, the spy opens clear 58-42493 communique, the spy opens clear 58-221254 communique, the spy opens clear 62-148295 communique, Te Kaiping 4-254545 communique, Te Kaiping 4-165041 communique, special fair 3-68939 communique, Te Kaiping 3-234594 communique, special fair 1-47545 communique, the spy opens clear 62-140894 communique, disclosed material in the middle of special fair 1-35910 communique and the special public clear 55-28874 communique etc.

Relate to JIS A 1070 aluminiums, what can be suitable for is to open flat 7-81264 communique, spy the spy to open flat 7-305133 communique, spy and open that flat 8-49034 communique, spy are opened flat 8-73974 communique, the spy opens flat 8-108659 communique and the spy opens disclosed material in the flat 8-92679 communique.

And relate to Al-Mg is alloy, and what can be suitable for is at the public clear 62-5080 communique of spy, special public clear 63-60823 communique, special fair 3-61753 communique, the spy opens clear 60-203496 communique, the spy opens clear 60-203497 communique, special fair 3-11635 communique, the spy opens clear 61-274993 communique, the spy opens clear 62-23794 communique, the spy opens clear 63-47347 communique, the spy opens clear 63-47348 communique, the spy opens clear 63-47349 communique, the spy opens clear 64-1293 communique, the spy opens clear 63-135294 communique, the spy opens clear 69-87288 communique, special fair 4-73392 communique, special fair 7-100844 communique, the spy opens clear 62-149856 communique, special fair 4-73394 communique, the spy opens clear 62-181191 communique, special fair 5-76530 communique, the spy opens clear 63-30294 communique, special fair 6-37116 communique, Te Kaiping 2-215599 communique, the spy opens disclosed material in clear 61-201747 communique etc.

Relating to Al-Mn is alloy, what can be suitable for is to open clear 60-230951 communique, spy the spy to open flat 1-306288 communique, spy and open flat 2-293189 communique, special public clear 54-42284 communique, special fair 4-19290 communique, special fair 4-19291 communique, special fair 4-19292 communique, spy and open that clear 61-35995 communique, spy are opened clear 64-51992 communique, the spy opens flat 4-226394 communique and United States Patent (USP) the 5th, 009,722 and 5, disclosed material in 028, No. 276 each specification.

Relating to Al-Mn-Mg is alloy, what can be suitable for is to open clear 62-86143 communique, spy the spy to open flat 3-222796 communique, special public clear 63-60824 communique, spy and open that clear 60-63346 communique, spy are opened clear 60-63347 communique, the spy opens flat 1-293350 communique, European patent the 223rd, No. 737, United States Patent (USP) the 4th, 818, No. 300 and BP wait disclosed material in each specification the 1st, 222, No. 777.

Relating to Al-Zr is alloy, can be suitable for be open clear 61-51395 communique the public clear 63-15978 communique of spy, spy, the spy opens clear 63-143234 communique and the spy opens disclosed material in the clear 63-143235 communique.

Relating to Al-Mg-Si is alloy, and what can be suitable for is in BP 1,421, disclosed material in 710.

As the aluminium alloy plate of support body for lithographic plate printing plate, generally contain fixed to some extent alloying component, be modulated to aluminium alloy solution, preferably this aluminium alloy solution is carried out purified treatment.

Above-mentioned purified treatment for the defective that prevents from metallic solution, to cause by foreign matters such as non-metallic inclusion and oxides, be dissolved in the defective that the gas (such as hydrogen) in the metallic solution causes and carry out.

Specifically, carry out the filter that the degassing that cosolvent handles, carries out with argon gas, chlorine is handled, made with filtering materials such as so-called hard medium filter such as earthenware filter, ceramic foam filter, alumina wafer, alumina globules, glass is disorderly handed over the filtration that filter etc. carries out or the combined treatment of the degassing and filtration etc.

Relate to filtration, open flat 6-57432 communique, spy the spy and open flat 3-162530 communique, spy and open flat 5-140659 communique, spy and open flat 4-231425 communique, spy and open that flat 4-276031 communique, spy are opened flat 5-311261 communique, the spy opens narration to some extent in the flat 6-136466 communique.

And relate to the degassing, can be suitable for be open flat 5-51659 communique the spy, reality is opened flat 5-49148 communique, the spy opens the content described in the flat 7-40017 communique.

Use has been carried out the aluminium alloy solution of purified treatment and has been cast.As the method for casting, having with the DC casting is the method for using stationary die of representative and with the method for continuous casting as the driving mold of representative.

When using the DC casting, preferably the cooling velocity with 0.5～30 ℃/sec is solidified aluminium alloy solution.If above-mentioned cooling velocity can form thick intermetallic compound less than 0.5 ℃/sec or above 30 ℃/sec.

Can make the cast block of thickness of slab 300～800mm with the DC casting.Top layer 1～the 30mm of the cast block that obtains, preferred 1～10mm must cut.Will carry out evenly heating before and after it if necessary handles.When carrying out the evenly heating processing, in order not make thickization of intermetallic compound, its temperature is taken as 450～620 ℃, and be 1～48hr heat time heating time.Heat time heating time is when being shorter than 1hr, the DeGrain that evenly heating is handled.

Then, carry out hot calender or cold pressing and prolong the calendering plate of making aluminium alloy.Before or after hot calender, perhaps in its process, preferably carry out intermediate annealing and handle.When intermediate annealing was handled, at 280～600 ℃ of 2～20hr down, preferably 350～500 ℃ of 2～10hr heating down, when using continuous annealing furnace, the programming rate heating with 10～200 ℃/sec can make the crystalline structure refinement when using periodic annealing furnace.

Obtain the wrought aluminum alloy sheets of thickness 0.1～0.5mm by above operation.Such aluminium alloy plate is preferably carried out carrying out flatness by apparatus for correcting such as roll planisher, pressure planishers improve processing.

Flatness is improved processing and also can be carried out after aluminium alloy plate is cut according to the size of determining, but in order to boost productivity, preferably carries out before cutting.

For aluminium alloy plate being processed as definite width, also can be with aluminium alloy plate by the rip cutting production line.And in order to prevent that aluminium alloy plate from damaging owing to rubbing each other, the surface that is preferably in aluminium alloy plate is coated with the thin oil film of last layer.To this oil film, volatile or nonvolatilely all be suitable for.Prolong to use to colding pressing and open disclosed method on the flat 6-210308 communique the spy.

In addition, for continuous casting process, having with Hunter (Hunter) method, 3C method is the method for the use chill roll of representative, is the use salband of representative or the method for cooling section etc. with Harry (Halle) method, Karst, Alps (ALUSUISSE CASTER) II type.When using continuous casting process, aluminium alloy solution is solidified with the cooling velocity of 100～1000 ℃/sec.In general, since faster than the cooling velocity of DC method, it is characterized in that solid solubility height with respect to the alloying component of aluminum matrix.What continuous casting process can be suitable for is, opens flat 3-79798 communique, spy the spy and opens flat 5-201166 communique, spy and open flat 5-156414 communique, spy and open flat 6-262203 communique, spy and open flat 6-122949 communique, spy and open flat 6-210406 communique, spy and open disclosed method in the middle of the flat 6-26308 communique etc.

Under the situation of using Hunter (Hunter) method,, can omit the operation of hot calender owing to can directly cast the cast sheet of thickness of slab 1～10mm continuously.

And under the situation of using Harry (Halle) method, because the cast sheet that can cast thickness of slab 10～50mm usually in the configuration hot calender roll subsequently of casting, can access the continuous casting calendering plate of thickness of slab 1～10mm.Such continuous casting calendering plate is identical with the DC casting, and passing through colds pressing prolongs, intermediate annealing, improve operations such as flatness, rip cutting production line, finally obtains the wrought aluminum alloy sheets of thickness of slab 0.1～0.5mm.

Relate to intermediate annealing condition, the rand spare of colding pressing when using continuous casting process, what can be suitable for is to open flat 6-220593 communique, spy the spy to open flat 6-210308 communique, spy and open flat 7-54111 communique, spy and open disclosed condition in the middle of the flat 8-92709 communique etc.

When the aluminium alloy plate with above-mentioned method manufacturing uses as support body for lithographic plate printing plate,, wish to have following various characteristic according to its purposes difference.

1. intensity:

In general, the support that support body for lithographic plate printing plate etc. use on galley,

Be necessary to have desirable intensity, specifically, preferred 0.2% proof stress is more than 140MPa.And in order to obtain having intensity to a certain degree after burning heat treatment, behind 270 ℃ of heating 3～10min, 0.2% proof stress is preferably more than 80MPa, more preferably more than 100MPa.

As open flat 7-126820 communique the spy, the spy opens in the clear 62-140894 communique disclosed, if in aluminium, add magnesium and manganese, its intensity can be improved, but, the addition of material and micro constitutent should be suitably selected according to different purposes because the comfort level that cooperates at printing machine version body descends.

2. crystalline structure:

The aluminium alloy plate that is obtained by DC casting and continuous casting process will carry out chemistry as described below, electrochemical surface treatment when making support body for lithographic plate printing plate.When carrying out such processing, if aluminium alloy plate surface crystallization tissue is oversize, owing to worry to cause that surface quality is bad, so the size of the crystalline structure on aluminium alloy plate surface is preferably not too big.The width of crystalline structure (minor axis) is preferably below 200 μ m, more preferably below 100 μ m, below 50 μ m.The length of crystalline structure (major axis) is preferably below 5000 μ m, more preferably below 1000 μ m, below 500 μ m.Opening flat 6-218495 communique, spy the spy opens flat 7-39906 communique, spy and opens and disclose relevant these content in flat 7-124609 communique etc.

3. distribute about alloying component:

When carrying out the processing of chemical surface treatment and electrochemical surface, if the composition on aluminium alloy plate surface is uneven, it is bad to worry that surface quality takes place, and preferably will carry out homogenising to the composition on surface.Opening flat 6-48058 communique, spy the spy opens flat 5-301478 communique, spy and opens and disclose relevant these content in the flat 7-132689 communique.

4. about intermetallic compound:

Chemical surface treatment, electrochemical surface are handled the influence of the size and the density that are subjected to intermetallic compound.Opening flat 7-138687 communique, spy the spy opens and discloses relevant these content in the flat 4-254545 communique.

The manufacture method of support body for lithographic plate printing plate

Support body for lithographic plate printing plate be with above-mentioned aluminium alloy plate as raw material, to make through surface roughening treatment process and anodic oxidation operation at least.

Below each treatment process is described.

The surface roughening treatment process

The surface roughening treatment process comprises electrolytic surface roughening operation and caustic corrosion treatment process at least.In a preferred embodiment of the invention, before above-mentioned electrolytic surface roughening operation, to carry out caustic corrosion treatment process (A).(order that promptly has caustic corrosion treatment process (A), electrolytic surface roughening operation and caustic corrosion treatment process (B)) preferably also comprises the surface roughening processing of machinery.

And, preferably set the pretreatment procedure of surface treatment procedure etc. as the preceding operation of above-mentioned mechanical surface roughening operation, as above-mentioned caustic corrosion treatment process (A) and/or back operation (B), preferably set the treatment process of removing powder bed.

Surface treatment procedure

Surface treatment procedure is to implement operation such as known ungrease treatment on above-mentioned aluminium alloy plate.Have again, in that worry will be through for a long time the time to carrying out surface treatment by making aluminium alloy plate, in order to prevent to damage, and will carry easily, preferably aluminium alloy plate is packed together.Regardless of concrete wrapping form, spread the material of buffering on the wooden cylinder such as aluminium alloy plate is placed on, externally wrap padded coaming, the iron bar of tying tight in the above, use the buffering annular slab at two ends, carry out as a whole, preferably the goods that bandage with packaging material are placed on the iron shelf of having laid padded coaming.Polyethylene film etc. can be used as packaging material, needle punched felt, hardboard etc. can be used as padded coaming.

Ungrease treatment is a rolling oil of removing the aluminium alloy plate surface, exposes clean aluminium alloy plate surface, and preferred arrangement is before the surface roughening treatment process and anodized operation of back operation.

As the solvent that uses in the ungrease treatment, can enumerate organic solvent, aqueous slkali, surfactant etc.

Concrete example as organic solvent, can enumerate oil series solvent, trichloro-ethylene, carrene, chlorinated polyvinyl chloride, 1 such as gasoline, kerosene, benzene, solvent naphtha, n-hexane, 1,1-trichloroethanes, Cui Si Linen (trade name of Trichlene trichloro-ethylene) are etc. chlorinated solvents.

As the object lesson of aqueous slkali, can enumerate the aqueous solution of alkali such as NaOH, sodium carbonate, sodium bicarbonate, sodium sulphate; Aqueous phosphatics such as sodium orthosilicate, sodium metasilicate, No. two sodium metasilicate, No. three aqueous silicate solutions such as sodium metasilicate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, sodium phosphate trimer, sodium pyrophosphate, sodium hexametaphosphate; Potassium hydroxide aqueous solution etc.When using the aqueous slkali degreasing,, be necessary suitably to set treatment conditions such as processing time, treatment temperature in order not make the aluminum alloy surface dissolving.

As the example of surfactant, can enumerate the aqueous solution of anion surfactant, cationic surfactant, non-ionic surface active agent, amphoteric surfactant etc., can use various commercially available commodity.

As the method for ungrease treatment, the handlebar aluminium alloy plate that can be suitable for immerse infusion process in the above-mentioned solvent, above-mentioned solvent spray to spraying process on the aluminium alloy plate, with the method for the wiping aluminium alloy plates such as cloth that contain solvent etc.

Yet when infusion process and spraying process, also can use ultrasonic wave.

Have again, relate to ungrease treatment, also be suitable for such as open the method for narrating in the flat 2-26793 communique the spy.

Mechanical surface roughening treatment process

In the surface roughening treatment process of machinery, as mechanical surface roughening processing method, the concavo-convex replica method of aluminium alloy plate arranged, utilize the method, hydro-abrasion method of roller brush etc., these methods can be used separately, also can unite use.

On aluminium alloy plate, duplicate in the concavo-convex method the preferred irregular roller etc. that uses from the teeth outwards.Roller is lip-deep concavo-convex, can be coated on the roller surface by microparticle and form by discharge processing, sandblast impact, laser, plasma etching, punch die, cutter etc.Convex-concave surface in formation can carry out known corrosion treatment, is preferably in to have fillet on the arris.Particularly to quench in order to improve hardness on the surface of roller, processing such as the chromium plating of hardening.

Give fine concavo-convex method to duplicating roller, be disclosed in the spy and open that flat 3-8635 communique, spy are opened flat 3-66404 communique, the spy opens on the clear 63-65017 communique, the method of using this roller to duplicate, be disclosed in the spy and open clear 55-74898 communique, spy and open clear 60-36195 communique, spy and open that clear 60-203496 communique, spy are opened flat 6-55871 communique, the spy opens on the flat 6-24168 communique, these all are suitable for reference.

Utilizing the method for metallic brush, is to walk on aluminium alloy plate on one side, on one side on the surface of aluminium alloy plate dispersed abrasive slurries (grinding-material) equably, add press contacts with the roller brush, with this roller brush from the teeth outwards revolution carry out the method that surface roughening is handled.

The crooked elastic rate of roller brush is preferably 10,000～40,000kg/cm ², more preferably 15,000～35,000kg/cm ², and its intensity is preferably 10～500g, more preferably 30～400g.

The material of roller brush can be enumerated synthetic resin and metal.As synthetic resin, can enumerate such as polyester such as polyolefin such as polyamide such as nylon, polypropylene, polyvinyl chloride, polybutylene terephthalate (PBT), Merlon etc.; And can enumerate stainless steel and brass etc. as metal.

And, can enumerate aphrolite, silica sand, aluminium oxide, silica, carborundum, silicon nitride etc. as the material of grinding-material.The granularity of grinding-material is preferably 5～80 μ m, more preferably 8～45 μ m.

The quantity delivered of the winding number of roller brush and crimp force, grinding-material etc. has no particular limits.

Carry out the device that this mechanical surface roughening is handled as being suitable for, such as enumerating at device and the described device of Fig. 1 described in the public clear 50-40047 communique of spy.Be equipped with on the described device of Fig. 1 and supporting aluminium alloy plate 101, press simultaneously the direction shown in the arrow carry a plurality of support roller 107 of aluminium alloy plate, on the figure to the entire upper surface of aluminium alloy plate 101 supply with two of grinding milk supply with parts 103, on the figure by supply with part 103 on the downstream side of the throughput direction of aluminium alloy plate 101 with contacted two rollers brush 102 of the upper surface of aluminium alloy plate 101.

Caustic corrosion treatment process (A)

In caustic corrosion treatment process (A), the purpose that caustic corrosion is handled is with the smooth smooth and homogenising of aluminium alloy plate etc.

As operable aqueous slkali in the caustic corrosion processing, except the caustic soda aqueous solution, can also enumerate sodium-salt aqueous solutions such as sodium carbonate, sodium bicarbonate, sodium sulphate; Sodium orthosilicate, sodium metasilicate, No. two sodium metasilicate, No. three aqueous silicate solutions such as sodium metasilicate; Aqueous phosphatics such as sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, sodium phosphate trimer, sodium pyrophosphate, calgon etc.The concentration of aqueous slkali is preferably 0.01～50wt%, and its pH value is preferably more than 11, more preferably more than 13.

Etching extent in caustic corrosion is handled is 1～20g/m ², etching extent is less than 1g/m ², handling forms concavo-convex by the mechanical surface roughening can not smoothing, can not form uniform groove in by electrolytic surface roughening operation in the operation of back, if etching extent is above 20g/m ², concavo-convex will the disappearance that forms previously.

The treatment conditions that caustic corrosion is handled will according to fixed etching extent (1～20g/m ²) carry out suitable selection, as a preferred example, the concentration of aqueous slkali is 0.01～50wt%, and fluid temperature is 20～90 ℃, and the processing time is 5sec～5min.

And, can enumerate infusion process, spray-on process etc. as the processing method that caustic corrosion is handled.In the middle of spray-on process, the aqueous slkali of spraying can be reclaimed recirculation.In the case, being accompanied by caustic corrosion handles, the composition of alkali such as the caustic soda in the aqueous slkali reduces gradually, and aluminum ions content increases gradually, in order to prevent to cause the variation of aqueous slkali amount and composition owing to factors such as water evaporates, preferably to suitably supply with aqueous slkali and water, remove the aluminium ion that reclaims in the aqueous slkali.

After caustic corrosion is handled, to remove totally with the aqueous slkali that the clamp roller is supplied with on aluminium alloy plate, preferably aqueous slkali not taken in below the operation.

As the device that carries out caustic corrosion, enumerate the device than as shown in FIG. 2.On the device shown in Fig. 2, form,, in corrosion treatment groove 211, move Yi Bian aluminium alloy plate is carried by supporting by roller 202 on one side by the driving force shown in the 222 figure ends by following each several part.This moment, the aqueous slkali by ejection in the shower nozzle 203 supplied on the width of aluminium alloy plate 222 equably, and aluminium alloy plate 222 is carried out corrosion, outside when mobile by etching tank 211, drained liquid by clamp roller 201, delivered to following operation.The solution of spraying returns accent liquid bath 205 by the bottom liquid back pipe 213 of corrosion treatment groove 211.

Transfer the solution part in the liquid bath 205 to be delivered in the nozzle 203 by arm 212 by infusion pump 204, a part is sent into diffusion dialysis groove 206, and a part is sent into and separated out groove 207.

Aqueous slkali after caustic corrosion is handled contains by the aluminium ion that dissolves on the aluminium alloy plate (sodium aluminate etc.).At this, from aqueous slkali, separate aluminium ion by diffusion dialysis groove 206.

Such as, under with the situation of the caustic soda aqueous solution, in diffusion dialysis groove 206, the caustic soda aqueous solution after the processing of sending here is dialysed as aqueous slkali, the caustic soda aqueous solution is separated with oversaturated sodium aluminate solution.In this diffusion dialysis groove 206,, add entry by feeding pipe 214 in order to replenish the water of evaporation.1. the caustic soda aqueous solution return in the accent liquid bath 205 by recovery tube 218 as reclaiming liquid.In this diffusion dialysis groove 206, about 70% in the treatment fluid of sending into reclaims as sodium hydroxide solution.On the other hand.Oversaturated sodium aluminate solution is sent into by dialysis waste liquid conveying pipe 215 as the dialysis waste liquid and is separated out groove 207.

In separating out groove 207, mix by the dialysis waste liquid of diffusion dialysis groove 206 with by the treatment fluid of transferring liquid bath 205, be nucleus with the aluminium hydroxide in the oversaturated sodium aluminate solution, from mixed liquor, carry out crystallization.Having removed aluminum ions sodium hydroxide solution is that master's the treatment fluid and the mixture of crystalline aluminum hydroxide are delivered in the thickener 208 through liquid pushing tube 216, the aluminium hydroxide of crystallization is then delivered to separated slurry in the drum filter 209 through piping 217, is collected in the hopper 210.In addition, based on the treatment fluid of the caustic soda aqueous solution, 2. return accent liquid bath 205 with pipe 219 through reclaiming liquid as reclaiming liquid.

In transferring liquid bath 205, except above-mentioned pipeline, replenish the caustic soda aqueous solution and water by

supply pipe

220 and 221 respectively.

In addition, variously operate adjusting by the valve that in the middle of pipeline, is provided with (not expression among the figure) for liquid measure and feeding time.

When the surface corrosion of being carried out aluminium alloy plate by above-mentioned aqueous slkali is handled, generate insoluble residue in its surface, promptly generate powder bed.At this, preferably in the operation of back, use and electrolyte (acid solution) that in electrolytic surface roughening treatment process, uses and acid solution with same composition, the operation of removing powder bed is set in the back operation of caustic corrosion treatment process.

Such as, when in electrolytic surface roughening operation, using nitric acid, just use nitric acid to go powder bed to handle, under the situation of using hydrochloric acid, just use hydrochloric acid to remove powder bed.

When removing powder bed, the temperature of liquid is preferably 30～80 ℃, and the processing time is preferably 3sec～3min.

Electrolytic surface roughening treatment process

Electrolytic surface roughening operation is for the photosensitive layer in the part that improves formation portrait on lithographic plate and the tackness of aluminium alloy plate, and in non-portrait part, improve full water-based, use as electrolyte, is carried out the operation that the electrolytic surface roughening is handled based on the acid solution of hydrochloric acid or nitric acid.As the kind of electrolysis, preferred alternating current electrolysis.In one embodiment of the invention, when using nitric acid to handle the electrolyte that uses in (below be called " electrolytic treatments ") as the electrochemical surface roughening, in this electrolyte, carry out electrolytic treatments by the electric current that replaces waveform, stop time in the electrolytic treatments is preferably below the 10sec, in 3 times, more preferably there is not the stop time in the electrolytic treatments or in 1sec.Electrolytic cell is handled the electrode shape of beginning part, and in order to suppress inhomogeneous with the rectangular processing section of aluminium alloy plate direct of travel, electrode is preferably taked the structure near aluminium.

The not rate of corrosion of electrolytic treatments is preferably below 30%.Rate of corrosion surpasses 30%, and the bonding bad of photosensitive layer and lithographic printing plate can be taken place, and makes printability resistance energy deterioration.

Here, as rate of corrosion not, be the ratio of surface area and the surface area that will carry out the aluminium alloy plate that the electrolytic surface roughening handles that does not carry out the aluminium alloy plate of corrosion treatment.

Particularly, be S with the area that carries out aluminium alloy plate 100 μ m * 100 μ m that the electrolytic surface roughening handles, the pore of obtaining on area S with SEM etc. forms projected area S ' partly, calculates with following formula:

Formula: (1-S '/S) * 100 (%)

The total electric weight of anode in the electrolytic surface roughening of electrolytic surface roughening treatment process is handled must have 50～800C/dm ², be preferably 50～400C/dm ²50～180C/dm more preferably ², be preferably 80～120C/dm especially ²If less than 50C/dm ², can not form uniform groove, if surpass 800C/dm ², then groove may be too big.

The ratio of total electric weight of anode and the total electric weight of negative electrode (the total electric weight of the total electric weight/anode of negative electrode) is preferably 0.7～1.0, and more preferably 0.85～0.97.Less than 0.7 o'clock, can not form uniform groove, surpassing 1.0 electrodes can dissolve.

Have again, the electrolyte layers of when the electrolytic surface roughening is handled, using, electrolyte by circulation constitutes, electrolyte mean flow rate when this circulate electrolyte is 500～4000mm/sec, be preferably 700～2500mm/sec, and transverse flow speed is distributed in above-mentioned flow velocity ± 50%, preferably in ± 30%.

If mean flow rate less than 500mm/sec, the inhomogeneous of surface quality can be taken place,, then be difficult to form uniform groove if surpass 4000sec.And if transverse flow speed distributes beyond above-mentioned ± 50%, it is inhomogeneous that the horizontal tone of base version will take place.

At this, the enough induced current formula current meters of the mean flow rate of electrolyte energy etc. are measured control.And transverse flow speed is distributed, be exactly the ratio of the variation of the mean flow rate of aluminium alloy plate running gear and Peak Flow Rate or minimum flow velocity.

Electrolytic treatments can be according to such as in the electrochemical roughening method described in the public clear 48-28123 communique of spy, No. 896563 specification of BP.This electrochemical 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.Also can use the spy and open the waveform described in the flat 3-79799 communique.

In electrolytic treatments, open clear 55-158298 communique the spy, the spy opens clear 56-28898 communique, the spy opens clear 52-58602 communique, the spy opens clear 52-152302 communique, the spy opens clear 54-85802 communique, the spy opens clear 60-190392 communique, the spy opens clear 58-120531 communique, the spy opens clear 63-176187 communique, Te Kaiping 1-5889 communique, Te Kaiping 1-280590 communique, Te Kaiping 1-118489 communique, Te Kaiping 1-148592 communique, Te Kaiping 1-178496 communique, Te Kaiping 1-188315 communique, Te Kaiping 1-154797 communique, Te Kaiping 2-235794 communique, Te Kaiping 3-260100 communique, Te Kaiping 3-253600 communique, Te Kaiping 4-72079 communique, Te Kaiping 4-72098 communique, the method of narrating in flat 3-267400 communique of narrating in the flat 1-141094 communique of Te Kaiping 3-267400 communique and Te Kai of Fang Tekai and the flat 1-141094 communique of Te Kai also can be suitable for.

As electrolyte, when using nitric acid, also can use specification 4,671,859,466 at United States Patent (USP), 576,4,661,219,4,618,405,462,628,4,600,482,4,566,960,4,566,958,4,566,959,4,416,972,4,374,710,4, the electrolyte of narration in the middle of 336,113,4,184,932 grades.

Concentration as the acid solution of electrolyte is preferably 0.5～2.5wt%, but considers the purpose of removing the powder bed that takes place when catholyte is handled, more preferably at 0.7～2.0wt%.Fluid temperature is preferably at 20～90 ℃, more preferably at 65～90 ℃.

The waveform of the alternating current that uses in electrolytic treatments can be enumerated trapezoidal wave, sine wave etc., wherein preferred trapezoidal wave.From the cost of supply unit, the frequency of alternating current is preferably 30～200Hz, more preferably 40～120Hz.The rise time Tp value of electrolysis power AC wave shape (when the waveform that uses alternating current is trapezoidal wave, being that electric current is by 0 time to peaking) is preferably below 2.0msec, more preferably at 0～1.2msec.The Tp value surpasses 2.0msec, and the influence of micro constitutent becomes big in the acid solution, is difficult to carry out uniform surface roughening and handles.

The efficient (duty) of the alternating current that uses in surface roughening treatment process as above, the viewpoint of the uniform outer surface roughening on the surface of aluminum plate is preferably in 0.25～0.5 scope, more preferably in 0.3～0.4 scope.So-called in the present invention efficient is meant in the period T of alternating current, and the time (anode reaction time) that anode reaction continues on the aluminium sheet is when being ta, the ratio ta/T that is got.Particularly, can generate composition on the surface of aluminum plate when carrying out cathode reaction based on the powder bed of aluminium hydroxide, make oxide film thereon dissolving and destruction, when carrying out later aluminium sheet anode reaction, in order to become the starting point of pit corrosion, the efficient of selection alternating current can increase the effect of uniform surface roughening.

Above-mentioned alternating electrical current promptly when the peak value of trapezoidal wave or square wave, promptly in the Iap of alternating current anodic cycle value, perhaps is preferably 10～200A/dm during the Icp value of cathode deposition period ², and Icp/Iap is preferably in 0.9～1.5 scope.In above-mentioned surface roughening operation, when the electrochemical surface roughening finished, the electric weight sum total that participates in the aluminium sheet anode reaction was preferably 50～800C/dm ²

The acid solution of Shi Yonging is that enough common DC currents of energy or alternating current carry out the material that the electrochemical surface roughening is handled, wherein preferred acid solution based on nitric acid in the present invention.Here " being main " is meant in solution and contains more than the 30wt% with respect to all compositions as the composition of main body, preferably contains more than the 50wt%.In other composition, also has identical meaning below.

The above-mentioned acid solution based on nitric acid is exactly to use DC current or alternating current can carry out the material that the electrochemical surface roughening is handled as mentioned above, such as, can be with in the nitrate such as aluminum nitrate, sodium nitrate, ammonium nitrate more than one,, add in the aqueous solution of nitric acid of concentration of nitric acid 5～15g/L and use when reaching capacity at 0.01g/L.In the above-mentioned acid solution based on nitric acid, also can dissolved iron, contained metal etc. in aluminium alloy such as copper, manganese, nickel, titanium, magnesium, silicon.

As above-mentioned acid solution based on nitric acid, contain nitric acid, aluminium salt and nitrate, and aluminum ions concentration is 1～15g/L, be preferably 1～10g/L, ammonium concentration is 10～300ppm, and preferred the use added the solution that aluminum nitrate and ammonium nitrate obtain in concentration of nitric acid is the aqueous solution of nitric acid of 5～15g/L.Above-mentioned aluminium ion and ammonium ion are the compositions of spontaneous increase when carrying out the processing of electrochemical surface roughening.

As electrolytic cell and power supply, all situations all can be suitable for, such as at United States Patent (USP) 4,203,637 specifications, the spy opens clear 56-123400 communique, the spy opens clear 57-59770 communique, the spy opens clear 53-12738 communique, the spy opens clear 53-32821 communique, the spy opens clear 53-32822 communique, the spy opens clear 53-32823 communique, the spy opens clear 55-122896 communique, the spy opens clear 55-132884 communique, the spy opens clear 62-127500 communique, Te Kaiping 1-52100 communique, Te Kaiping 1-52098 communique, the spy opens clear 60-67700 communique, Te Kaiping 1-230800 communique, Te Kaiping 3-257199 communique, the spy opens clear 52-58602 communique, the spy opens clear 52-152302 communique, the spy opens clear 53-12739 communique, the spy opens clear 53-32833 communique, the spy opens clear 53-32824 communique, the spy opens clear 53-32825 communique, the spy opens clear 54-85802 communique, special public clear 48-28123 communique, special public clear 51-7081 communique, the spy opens clear 52-138838 communique, the spy opens clear 52-133840 communique, the spy opens clear 52-133844 communique, the spy opens clear 52-133845 communique, the spy opens clear 58-149135 communique, the spy opens the form of being given an example in the clear 54-146234 communique.

Certainly, can use as shown in Figure 3 device.

Have 302, the second processing sections 303, first processing section and the 3rd processing section 304 at device shown in Figure 3.This first, second and the 3rd processing section 302,303 and 304 each have electrolytic cell 305.In electrolytic cell 305, installed a pair of circular-arc main electrode 306 that is connected on the AC power (on the figure show) and can free rotating drum 307, between main electrode 306 and drum 307, filled electrolyte 308 in the main electrode inboard.

Electrolyte 308 is by not shown pump circulation.In order to circulate, the flow velocity of electrolyte must reach 500～4000mm/sec, preferred 700～2500mm/sec.If in above-mentioned scope, carry out circulate electrolyte, the inhomogeneous of surface quality can not taken place, obtain to form the effect of even groove.

The direct of travel of the loop direction of electrolyte 308 and aluminium alloy plate 301 can be parallel or opposite.

Aluminium alloy plate carries out electrolytic treatments limit by the driving force that does not show on the figure by limit, first processing section by a plurality of rollers supports of advancing and moves to the 3rd processing section.The modes of emplacement of aluminium alloy plate 301 at this moment is, the contact-making surface 301b of the drum 307 of first processing section 302 delivered to the drum 307 of second processing section 303 contact.Advance and between second processing section 303 and the 3rd processing section 304, design to reverse, for this reason, the modes of emplacement of aluminium alloy plate 301 is, with 307 contacted opposite face 301a of drum of first processing section 302 and second processing section 303, when delivering to the 3rd processing section 304 just and drum 307 contact.Electrolytic treatments has just all been carried out in the two sides of aluminium alloy plate like this.

Make aluminium alloy plate be in frequent wetting state on the aluminium alloy plate 301 for electrolyte in the distance 310 of advancing in counter-rotating is dispersed in, design several shower nozzles 311.

Between the first and second above-mentioned electrolytic treatments, on aluminium alloy plate, carry out catholyte and handle.Catholyte is handled thus, generates powder bed on the aluminium alloy plate surface, produces hydrogen simultaneously and can carry out more uniform electrolytic surface roughening.

Such catholyte is handled, and the cathode capacity when carrying out in above-mentioned acid solution is preferably 3～80C/dm ², 5～30C/dm more preferably ²Cathode capacity is less than 3C/dm ²The time, the adhesion amount deficiency of powder bed, and surpass 80C/dm ²The time, the adhesion amount surplus of powder bed is not preferred yet.

The electrolyte that catholyte handle to use if contain hydrochloric acid and at least a acid solution of nitric acid just better, can enumerate as the electrolyte of first and second electrolytic treatments and to have narrated, and the solution that uses in first and second electrolytic treatments identically or different all is fine.

Handle by above-mentioned electrolytic surface roughening, on the aluminium alloy plate surface, can form average trench diameter 0.1～1.2 μ m, the groove of average gash depth 0.05～0.6 μ m.If formed such groove, just can stably make support with excellent in resistance brush property, stain resistance.

For average trench diameter, can obtain the mean value of the projection circle equivalent diameter of the groove that in the scope of 100 μ m * 100 μ m, exists such as the photo that obtains with SEM photographies such as (500～3000 times).

And average gash depth is the photo that obtains with atomic force microscope photographies such as (50～5000 times), obtains the mean value of the gash depth that exists in the scope of 100 μ m * 100 μ m.

Through the aluminium alloy plate of electrolytic surface roughening treatment process, preferably to carry out caustic corrosion operation (B) with the same purpose of having narrated of caustic corrosion operation (A).

Particularly, preferably carry out caustic corrosion operation (B) with the aqueous slkali of pH value more than 11.The aqueous slkali of pH value more than 11 that uses in this caustic corrosion operation (B) can use the aqueous slkali that uses in the caustic corrosion operation of having narrated (A).

Handling the etching extent that obtains by above-mentioned caustic corrosion is 0.01～1.0g/m ²If etching extent is less than 0.01g/m ², being difficult to control meltage, the end of the groove that is obtained by the electrochemical surface roughening can not smoothing, in addition, if surpass 1.0g/m ², the end of groove is too smooth, and surface area also can reduce.

On the surface of handling the aluminium alloy plate that obtains by caustic corrosion, can generate powder bed.Therefore, as the back operation of this caustic corrosion treatment process, preferably be provided with one remove powder bed go the powder bed treatment process.Go in the powder bed treatment process at this, preferably remove powder bed (going powder bed to handle) with the solution that contains sulfuric acid.The solution that contains sulfuric acid except sulfuric acid, suitably can contain phosphoric acid, nitric acid, chromic acid, hydrochloric acid etc.Going in the powder bed processing method of the such sulfur acid solution of use, be to open the method described in the clear 53-12739 communique the spy such as what can be suitable for.

Yet this goes powder bed to handle, and as opening such as the spy described in the clear 56-51388, carries out with the alkali treatment combination.

Particularly, the spy open clear 60-8091 communique, spy open clear 63-176188 communique, spy open flat 1-38291 communique, spy open flat 1-127389 communique, spy open flat 1-188699 communique, spy open flat 3-177600 communique, spy open flat 3-126891 communique, spy open flat 3-191100 communique etc. in the middle of described method can unite use with the method for removing powder bed.

Anodized

Below, carry out anodized (anodized operation) to aluminium alloy plate.Form anodic oxidation coating on the top layer of aluminium alloy plate thus.Anodized, is handled by electric current as anode with aluminium alloy plate in electrolyte.Anodized is not only carried out once, preferably carries out repeatedly.

As electrolyte, except sulfuric acid, phosphoric acid, oxalic acid, can use in chromic acid, amidosulfonic acid, sulfanilic acid, the benzene sulfonic acid at least aly, it is better to contain aluminium ion.Particularly, the concentration of aluminium can preferably be used the sulfuric acid of 50～300g/L below 5wt%.Wherein in above-mentioned sulfuric acid, can contain phosphoric acid, chromic acid, oxalic acid, sulfanilic acid, benzene sulfonic acid etc.

The amount of the anodic oxide coating that forms is preferably at 1.0g/m ²More than, 1.0～5.0g/m more preferably ², be preferably 1.5～4.0g/m especially ²If the amount of anodic oxide coating is less than 1.0g/m ², damaged surfaces takes place easily.

Anodised treatment conditions have many variations owing to the electrolyte that uses is different, cannot treat different things as the same, but respectively the temperature of electrolyte is controlled at 5～70 ℃ scope at least by thermometer, conductivity gauge and densimeter, the electrical conductivity of electrolyte is controlled at the scope of 0.1～0.9S/cm, the specific gravity control of electrolyte in 1.05～1.20 scope.At least will be in above-mentioned scope the temperature of electrolyte, electrical conductivity and specific gravity control, the amount that makes oxide film thereon can form the uniform film that the tunicle defective does not take place in above-mentioned scope.Preferably making the concentration of electrolyte by titrator and conductivity gauge etc. is 1～80wt%, and voltage is 1～100V, and electrolysis time is 15sec～50min.

The electrolyte mean flow rate is necessary for 10～2500mm/sec, is preferably 20～1000mm/sec.When the flow velocity of electrolyte during less than 10mm/sec, can heating on the interface of aluminium alloy plate, cause the inhomogeneous of surface quality, if it is surpass 2500mm/sec, then black.

And transverse flow speed distribute must the electrolyte mean flow rate ± 50% in, preferably in ± 30%.If transverse flow speed is distributed in beyond electrolyte mean flow rate ± 50%, can become that the lateral surfaces quality is inhomogeneous, the uneven reason of tone.

Current density is necessary for 2～50A/cm ², be preferably 5～50A/cm ²Current density is less than 2A/cm ²The time, the production rate of epithelium is low, surpasses 50A/cm ²The time, make the unglazed or generation dim spot of epithelium owing to burn.

Under the situation of carrying out repeatedly anodized, the current density of initial operation preferably final operation current density 1～50%, more preferably 1～45%, be preferably 1～40% especially.If the current density of initial operation surpasses 50% of final operation current density, laterally just can not form uniform epithelium at aluminium alloy plate, then productivity ratio is low less than 1%.Particularly, the current density of initial operation is preferably 3～20A/cm ², 5～15A/cm more preferably ²

Anodized in the present invention, in satisfying the limit of above-mentioned condition, open clear 54-81133 communique the spy, the spy opens clear 57-47894 communique, the spy opens clear 57-51289 communique, the spy opens clear 57-51290 communique, the spy opens clear 57-54300 communique, the spy opens clear 57-136596 communique, the spy opens clear 58-107498 communique, the spy opens clear 60-200256 communique, the spy opens clear 62-136596 communique, the spy opens clear 63-176494 communique, Te Kaiping 4-176897 communique, Te Kaiping 4-280997 communique, Te Kaiping 6-207299 communique, Te Kaiping 5-24377 communique, Te Kaiping 5-32083 communique, Te Kaiping 5-125597 communique, described method can be suitable in the middle of the Te Kaiping 5-195291 communiques etc.As the device that carries out anodized, can use such as anodized device 410 shown in Figure 4.

Anodized device shown in Figure 4 has been equipped the electrolytic treatments groove 414 that stores the electric groove 412 of giving of electrolyte 418 and store electrolyte 419.In giving electric groove 412, disposed and given electrode 420, in electrolytic treatments groove 414, disposed electrolysis electrode 430-1～430-3 respectively, these insert below the liquid level that is configured in electrolyte 418 and 419 for electrode 420 and electrolysis electrode 430-1～430-3, dispose two rollers 422 respectively in giving electric groove 412 and electrolytic treatments groove 414.Disposed the position clamp roller 424 higher between roller 422 in giving electric groove 412 and the roller 422 in the electrolytic treatments groove 414 than roller 422, the direction of aluminium alloy plate 416 arrow in the figure is carried, immerse in the electrolyte of giving in the electric groove 412 418, immerse after on clamp roller 424, removing liquid in the electrolyte 419 in the electrolytic treatments groove 414, send into next process.Connect dc source 434-1～434-3 respectively for electrode 420 and electrolysis electrode 430, aluminium alloy plate 416 in giving electric groove 412 by giving electrode 420 lotus that becomes positively charged, be with negative electrical charge by electrolysis electrode 430-1～430-3 then, form anodic oxide coating in its surface.Near electrolysis electrode 430-1～430-3, be called first section, second section and the 3rd section.

Also can use and open clear 48-26638 communique, spy the spy and open clear 47-18739 communique and the disclosed device of special public clear 58-24517 communique.

By the anodic oxide coating that above-mentioned anodized obtains, be preferably formed more than the average diameter 3nm 100/μ of density m ²Above micropore.Average diameter is during less than 3nm, and tackness is bad, and density is less than 100/μ m ²The time, immersion property, tackness are all poor.The density of micropore by anodized after 100,000 times-200,000 times the electron scanning micrograph on aluminium alloy plate surface measure.After measuring the area of each micropore, with square just the obtain diameter of this area divided by pi.Accelerating potential is suitable more than 5kV.

After the anodized,, preferably carry out sealing of hole and handle in order to make aluminium alloy plate and layer tackness in the above best.Before handling, sealing of hole want the antianode oxide scale film to corrode.The method and apparatus that sealing of hole is handled can use as open flat 4-4194 communique, spy the public clear 56-12518 communique of spy, spy and open flat 5-202496 communique, spy and open flat 5-179482 communique, spy and open described in the specification such as flat 6-154853 communique and at the method and apparatus described in Fig. 5.

At the device shown in Fig. 5, equipped and cut two sulculuses 6 and 7 that section roughly is J-shaped along the vertical direction open.These two sulculuses 6 and 7 long wall 6A and 7A are configured in the inboard, and these two wall 6A are linked to each other by the lower wall 11 of horizontal positioned with 7A.In the part of this lower wall 11 and wall 6A and 7A, being covered with section configuration is the upper wall 9 of コ shape.In sulculus 6 and 7, and the next door of lower wall 11 and wall 6A or the formed sweep of wall 7A has disposed several rollers 8 of several conveying aluminium alloy plate 1 usefulness.Between the roller that lower wall 11 and wall 6A or the formed sweep of wall 7A are disposed nearby, at the nozzle 2 of the several supply steam of transport path upper and lower settings of aluminium alloy plate 1.Storing liquid in sulculus 6,7, by between the liquid level of configuration between wall 6A, 7A and the upper wall 9 is with wall 6A, 7A and lower wall 11 and the space sealing that forms between the upper wall 9, this space is just as vaporium.Aluminium alloy plate 1 changes direct of travel by roller 8, at first in sulculus 6, lead, liquid level between liquid level in sulculus 6 and the steam indoor gas 4 places that promptly enter the mouth enter vaporium, carrying out sealing of hole by steam between vaporium handles, the interface of liquid level is outlet 5 in gas in the vaporium and the sulculus 7, outwards guides in sulculus 7 thus and enters next device.

In the middle of sealing of hole is handled, except above-mentioned steam, also use liquid such as hot water, normal-temperature water.These liquid can use pure water, also can be contain the oxyacid of the oxyacid of organic solvent, amines, organic acid, phosphorus and salt thereof, free oxyacid and salt thereof, boron and salt thereof etc. at least a.

The index of sealing of hole is used sealing of hole rate (slip of expression oxide scale film), with [formula of (the oxide scale film surface area before the sealing of hole)-(surface area of sealing of hole rear oxidation epithelium) * 100/ (oxide scale film surface area before the sealing of hole) is obtained.Above-mentioned surface area is made with Quantasorb[Kan Tasuofu (カ Application ソ one プ), the shallow Ai Ounikusi of soup (アイオニ Network ス) (strain) preferably with simple and easy BET method] obtain.In the present invention, handle the necessary surface area that reduces oxide scale film more than 30% by sealing of hole, preferred 1～1000esc of processing time.

Aluminium alloy plate after sealing of hole is handled can carry out United States Patent (USP) 2,946, No. 638 the described fluorine calcium zirconate of specification is handled, United States Patent (USP) 3,201, phosphomolybdate described in No. 247 specifications is handled, british patent specification 1,108, alkyl titanate described in No. 559 is handled, German patent specification 1,091, polyacrylic acid described in No. 433 is handled, German patent specification 1,134, No. 093 and british patent specification 1,230, polyvinylsulfonic acid described in No. 447 is handled, sulfonic acid described in the special public clear 44-6409 communique is handled, US Patent specification 3,307, phytic acid described in No. 951 is handled, the spy opens in the clear 58-16893 communique and special processing of opening oleophylic organic high molecular compound described in the clear 58-18291 communique and divalent slaine, as United States Patent (USP) 3,860, No. 426 specification is described, the hydrophilic cellulose (such as carboxymethyl cellulose) that will contain water-soluble metal salt (such as zinc acetate) is as its priming coat, open described in the clear 59-101651 communique hydrophilicity-imparting treatment of carrying out as priming coat with the water-soluble polymer that contains sulfonate radical as the spy, open phosphate described in the clear 62-19494 communique as the spy, the spy opens the soluble epoxide compound described in the clear 62-33692 communique, open the phosphoric acid modification starch described in the clear 62-97892 communique as the spy, the spy opens amino acid whose salt or the ester described in the clear 63-56498 communique, the spy opens the organic sulfonic acid that contains carboxyl or hydroxyl described in the clear 63-145092 communique, the spy opens amino and the sulfonic compound of having described in the clear 63-165183 communique, specific carboxylic acid derivates described in the Te Kaiping 2-316290 communique, phosphate described in the Te Kaiping 3-215095 communique, having an amino and having the compound of phosphorous oxyacid acidic group described in the Te Kaiping 3-261592 communique, aliphatic or aromatic sulphonic acids such as benzene sulfonic acid described in the Te Kaiping 5-246171 communique, sulfur-containing compounds such as thiosalicylic acid described in the Te Kaiping 1-307745 communique, the compound with phosphorous oxyacid acid group described in the Te Kaiping 4-282637 communique is as priming coat, the spy opens the acid dyes described in the clear 60-64352 communique and carries out painted etc.

To support of the present invention, can be arranged on the master that the photosensitive layer of giving an example is below made plate printing plate of the present invention.Expose on the master of this plate printing plate and development etc., the image of formation can use for printing, and obtaining this state just becomes plate printing plate.As above-mentioned photosensitive layer, can be the photosensitive layer that directly writes down infrared laser, but be not limited thereto, enumerate so example of photosensitive layer below.

[I] contains the ester of o-naphthoquinone two azide and the photosensitive layer of alkali soluble resins:

As the ester of o-naphthoquinone two azide, preferred o-naphthalene quinone di-azide sulfonic acid ester or the o-naphthoquinones two nitrine sulfonic acid amides of o-naphthoquinones two nitrine carboxylates and aromatic amines compound or the acid amides of o-naphthoquinones two nitrine carboxylic acids.

And as alkali soluble resins, can enumerate lacquer resins such as phenolic resins, o-CF, m-CF, be more preferably especially the above-mentioned phenolic resins described in No. 4028111 specifications of United States Patent (USP) and as the phenol of the alkyl replacement of 3～8 carbon atoms of usefulness of tert-butyl benzene fluosite or the condensation product of CF use together.

To such compound, particularly in order the time to form visible image in exposure, the inorganic anion salt, three halogen that add o-naphthoquinones two triazo-compounds, 4-sulfonic acid chloride, p-azoic diphenylamine for first oxadiazole compound, have a benzofuran ring three halogen for first oxadiazole compound etc.Can add various dyestuffs as colouring agent.

On the photosensitive layer that forms, above-mentioned various compositions are dissolved in solution coat that solvent obtains on support.The solvent of Shi Yonging here, can use dichloroethanes, cyclohexanone, MEK, glycol monoethyl ether, ethylene glycol monoethyl ether, 2-Methoxy acetic acid ethyl ester, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide (DMSO), dimethylacetylamide, dimethyl formamide, water, N-methyl pyrrolidone, oxolane alcohol, acetone, DAA, methyl alcohol, ethanol, isopropyl alcohol, diethylene glycol dimethyl ether etc., these solvents can be used alone or as a mixture.

The photosensitive composition that is obtained by these compositions is with solids content 0.5～3.0g/m ²Be coated on and produce photosensitive layer on the support.

The photosensitive layer of relevant [I], the spy that the inventor applied in the past opens in the flat 11-84675 communique and once described in detail in [0027]～[0028] section.

[II] contains diazo resin and has the photosensitive layer of water-insoluble oleophylic macromolecular compound:

As diazo resin, can enumerate the reaction product that can be dissolved in organic solvent that generates such as the condensation polymer of p-diazonium diphenylamines and formaldehyde or acetaldehyde and hexafluorophosphate, tetrafluoroborate, be the diazo resin inorganic salts, aforesaid condensation polymer and sulfonic acid class such as P-toluenesulfonic acid or its salt, phosphine class such as phenyl-phosphonic acid or its salt, contain the compound of hydroxyl such as 2, the product of 4-resacetophenone, 2-hydroxyl-4-methoxyacetophenone-5-sulfonic acid or its reactant salt promptly dissolves in the diazo resin acylate of organic solvent etc.

In the present invention, other diazo resin that may be fit to use is aromatic compound and the diazo compound with organic group at least a in carboxyl, sulfonic group, sulfinic acid base, phosphorous oxyacid acidic group and the hydroxyl, the optimization aromatic diazo compound is as the cocondensation compound of construction unit, as the preferred phenyl of this aromatic ring, naphthyl.

The diazo resin of Shi Yonging in the present invention according to the mole of various monomers condensation condition difference when, can obtain the molecular weight of arbitrary value, for the molecular weight for application target of the present invention effectively is about 40-100, and 000, preferably approximately 800～8,000.

As having water-insoluble oleophylic macromolecular compound, can enumerate with the monomer shown in following (1)～(17) as its construction unit, molecular weight is generally 1～200,000 copolymer.

(1) have acrylic amide, methacryl amine, esters of acrylic acid, methyl acrylic ester and the hydroxy styrenes class of aromatic hydroxyl, such as N-(4-hydroxy phenyl) acrylamide or N-(4-hydroxy phenyl) Methacrylamide, o-, m-, p-hydroxy styrenes, o-, the m-of acrylic or methacrylic acid, p-hydroxy phenyl ester;

(2) have the esters of acrylic acid and the methacrylate of aliphatic hydroxyl, such as the 2-hydroxy methacrylate of acrylic or methacrylic acid, the 4-hydroxyl butyl ester of methacrylic acid;

(3) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, itaconic acid;

(4) acrylic acid (replacement) Arrcostabs such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, cyclohexyl acrylate, 2-ethyl hexyl acrylate, benzyl acrylate, acrylic acid-2-chloroethene ester, glycidyl acrylate, acrylic acid N-dimethylamino ethyl ester;

(5) (replacement) Arrcostab of methacrylic acids such as methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, cyclohexyl methacrylate, benzyl methacrylate, GMA, methacrylic acid N-dimethylamino ethyl ester;

(6) acrylamide or methacryl amines such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-hexyl methyl acrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide N phenyl acrylamide, N-nitrobenzophenone acrylamide, N-ethyl-N phenyl acrylamide;

(7) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ethers, ethoxy vinyl ethers, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ethers, Vinyl phenyl ether;

(8) vinyl esters such as vinylacetate, vinyl chloroacetate, vinyl butyrate, benzoic acid vinyl acetate;

(9) phenylethylenes such as styrene, AMS, 1-chloro-4-methyl-benzene;

(10) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone;

(11) olefines such as ethene, propylene, isobutene, butadiene, isoprene;

(12) N-vinyl pyrrolidone, N-VCz, 4-vinylpridine, acrylonitrile, methacrylonitrile etc.;

(13) unsaturated acid imides such as maleimide, N-acryloyl group Methacrylamide, N-acetyl group Methacrylamide, N-propyl methyl acid amides, N-(p-benzyl chloride base) Methacrylamide;

(14) N-(o-aminosulfonyl phenyl)-Methacrylamide, N-(m-aminosulfonyl phenyl)-Methacrylamide, N-(p-amino) sulfonyl-phenyl Methacrylamide, N-(1-(3-aminosulfonyl)-naphthyl)-Methacrylamide, methacryl amines such as N-(2-aminosulfonyl ethyl) Methacrylamide, and having and top described identical substituent acrylic amide, and methacrylic acid-o-aminosulfonyl phenyl ester, methacrylic acid-m-aminosulfonyl phenyl ester, methacrylic acid-p aminosulfonyl phenyl ester, methyl acrylic esters such as methacrylic acid 1-(3-aminosulfonyl naphthyl) ester and have unsaturated sulfonamide such as substituent esters of acrylic acid same as described above;

(15) N-(2-(methacryloxy)-ethyl)-2,3-dimethyl maleimide, cinnamic acid vinyl esters etc. contain the unsaturated monomer of crosslinked group on side chain, but also the monomer copolymerization that can obtain with top monomer copolymerization;

(16) phenolic resins described in No. 3751257 specifications of United States Patent (USP) and such as polyvinyl acetal resinoids such as polyvinyl methylal resin, polyvinyl butyral resins;

(17) alkali-soluble polyurethane is opened clear 60-182437 communique, spy and is opened clear 62-58242 communique, spy and open clear 62-123452 communique, spy and open that clear 62-123453 communique, spy are opened clear 63-113450 communique, the spy opens the macromolecular compound described in the flat 2-146042 communique as opens clear 57-904747 communique, spy the public clear 54-19773 communique of spy, spy.If necessary, can in above-mentioned copolymer, add polyvinyl butyral resin, polyurethane resin, polyamide, epoxy resin, lacquer phenolic resins, natural resin etc.

In such photosensitive composition that contains these compositions, can use the known additive identical together according to purpose with the front.The solids content of photosensitive composition can be dissolved in appropriate solvent in 1～50wt% scope, the solids content on support is generally 0.2～10g/m ², preferably at 0.5～3g/m ²Scope in coating make photosensitive layer.

About photosensitive layer [II], the detailed narration of [0029]～[0035] Duan Zhongyou that the previous spy who proposes of the inventor opens flat 11-84675 communique.

[III] contains the photosensitive layer of photodimerization type photosensitive composition and photo-polymerization type photosensitive composition:

As photodimerization type photosensitive composition, can enumerate the polymer that on side chain or main chain, has dimaleoyl imino and cinnamyl, cinnamoyl, cinnamylidene, cinnamylidene butyl and chalcone base etc.Because these polymer have solubility and swelling in buck, operablely in polymer, contain carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acids and their alkali metal salt and ammonium salt in addition, and the compound of the acidic group of buck dissociation constant pKa value 6～12.As required, also can make 13 kinds of monomers with above-mentioned acidic group, monomer carry out copolymerization with maleimide base group.

In containing the photosensitive layer of these compounds, can use sensitizers such as benzophenone derivates, benzanthrone derivative, quinones, aromatic nitro compound, naphthothiazoles quinoline derivant.

As the photo-polymerization type photosensitive composition, can enumerate the acid amides etc. of ester, unsaturated carboxylic acid and the aliphatic polyamine of unsaturated carboxylic acid and salt thereof, unsaturated carboxylic acid and aliphatic polyol.

As photopolymerisable initator, can use combination, benzothiazole based compound, the trihalomethyl group-known initators such as s-triaizine compounds of alpha-carbonyl compound, polynucleation quinone compound, triallyl imidazoles dimer/p-aminophenyl ketone.And meanwhile, as having buck solubility or swelling, and can film forming high molecular polymer, the copolymer, methacrylic acid/methyl methacrylate (or methacrylate) copolymer that can enumerate (methyl) benzyl acrylate/(methyl) acrylic acid/other necessary polyaddition type vinyl monomer carries out the compound of half esterization and acid ethylenic copolymer etc. with pentaerythritol triacrylate on copolymer-maleic anhydride.

[IV] electronic photography photosensitive layer:

Such as, can use at United States Patent (USP) 3, disclosed ZnO photosensitive layer on 001, No. 872 specification also can use and open clear 56-161550 communique, spy the spy and open the photosensitive layer that clear 60-186847 communique, spy are opened the use electronic photography photoreceptor described in clear 61-238063 communique etc.

The amount of the photosensitive layer of setting on support, the dry weight in after the coating is about 0.1～7g/m ², preferably at 0.5～4g/m ²Scope.

About the photosensitive layer of [III] or [IV], open the original spy who proposes of the inventor that [0036]～[0040] section has detailed narration in the flat 11-84675 communique.

In the middle of such photosensitive layer, can enumerate (1) as representative and contain infrared absorbent, produce acid or the compound of free radical and the negative-type photosensitive layer that can maybe can carry out the compound of radical polymerization by the crosslinked compound of acid by heat, perhaps (2) contain infrared absorbent, by the acidic compound of heat, have the positive type photosensitive layer that the compound of key is decomposed in acid.Negative-type photosensitive layer and positive type photosensitive layer are described respectively below.

(1) negative-type photosensitive layer:

A kind of as in such negative-type photosensitive layer enumerates the example of photopolymerization layer.On photopolymerization layer, contain (A) infrared absorbent, and (B) free radical generating agent (free radical polymerization initiator) and cause polymerisation and the radical polymerization type compound (C) that hardens by the free radical that produces, (D) bonding polymer preferably also contained.Infrared absorbent changes the infrared ray that absorbs into heat, and decompose the free radical polymerization initiator of salt etc. by the heat that produces this moment, produces free radical.The unsaturated double-bond that radical polymerization type compound has at least one ethene is selected from and has at least one, the compound of preferred plural ethene unsaturated bond end group, and by the free radical generation link formation polymerisation that produces, thus sclerosis.

Enumerate sour cross-linked layer as an embodiment beyond the photosensitive layer.On sour cross-linked layer, contain (E) by light or hot acidic compound (hereinafter referred to as acid-producing agent), and (F) carry out crosslinked compound (below be referred to as crosslinking agent) by the acid that produces, particularly in order to form the layer that contains these compounds, also contain in the presence of acid (G) alkali-soluble polymer that can react with crosslinking agent.At so sour cross-linked layer, by illumination or heating acid-producing agent is decomposed and produce acid, impel the crosslinking agent activation, between crosslinking agent itself or crosslinking agent and bonding polymer, form firm cross-linked structure, make alkali solubility reduce thus, in developer, become and do not dissolve.At this moment, in order to use the infrared laser energy effectively, in photosensitive layer, to cooperate (A) infrared absorbent.

Be described in all cpds that negative-type offset printing plate originals recording layer uses below.

(A) infrared absorbent

As the photosensitive layer of offset printing plate originals, have may construct in the present invention with the infrared laser recording image of launching.On such photosensitive layer, preferably use infrared absorbent.Infrared absorbent has the function that the infrared ray that will absorb is converted to heat.The heat that produces in the time of is thus decomposed free radical generating agent and acid-producing agent, produces free radical or acid.The infrared absorbent of Shi Yonging is dyestuff or the pigment that absorption maximum is arranged to the 1200nm place at wavelength 760nm in the present invention.

As dyestuff, can use commercially available dyestuff or at the known dyestuff described in " dyestuff brief guide " documents such as (Synthetic Organic Chemistry association compile, clear and 45 years versions).Particularly, can enumerate the spy and open flat 10-39509 communique, the dyestuff described in segment number [0050]～[0051].

As particularly preferred in this class dyestuff, can enumerate anthocyanidin, this storehouse Li Liwumu (ジ Network ワリリウ system) pigment, pyrroles's salt, mercaptan nickel complex etc.Preferred anthocyanidin, the particularly anthocyanidin of following general formula most preferably:

General formula (I)

In general formula (I), X ¹The expression halogen atom is perhaps represented X ²-L ¹, X here ²Be oxygen atom or sulphur atom, L ¹The alkyl of 1～12 carbon atom of expression.R ¹And R ²The alkyl of representing 1～12 carbon atom independently of one another.For the consideration of the storage stability of photosensitive layer coating liquid, R ¹And R ²Above alkyl of 2 carbon atoms preferably, and R ¹And R ²Interosculate, it is particularly preferred forming 5 yuan of rings or 6 yuan of rings.

Ar ¹, Ar ²Each other can be identical or different, expression preferably has substituent aromatic hydrocarbyl.Y ¹, Y ²Each other can be identical or different, expression sulphur atom or carbon number 12 following dialkyl group methylene.R ³And R ⁴Each other can be identical or different, expression preferably has substituent carbon number at the alkyl below 20.As preferred substituted, can enumerate 12 carbon atoms following alkoxyl, acyloxy, sulfo group.R ⁵, R ⁶, R ⁷And R ⁸Separately can be identical or different, expression hydrogen atom or 12 alkyl that carbon atom is following.The consideration that obtains easily for raw material, preferably hydrogen atom.And Z ^1-Represent corresponding anion.But, at R ¹～R ⁸All under the situation about being replaced by sulfo group, Z ^1-There is no need.For the consideration of photosensitive layer coating stability, preferred Z ^1-Can be halide ion, cross chlorate ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, and sulfonate ion, preferred especially chlorate ions, hexafluorophosphoricacid acid ions and the allyl sulphonic acid ion crossed.

In the present invention, as the object lesson of the anthocyanidin shown in the general formula that can be suitable for (I), can enumerate the spy and be willing to the compound described in paragraph [0017]～[0019] in the flat 11-310623 specification.

As the dyestuff that uses in the present invention, (Japanese pigment technology association compiles can to use commercially available dyestuff or color to instruct brief guide " up-to-date pigment brief guide ", version in 1997), (CMC publishes " up-to-date pigment applications technology ", version in 1986) and the pigment described in " printing-ink technology " (CMC publish, version in 1984).

As the kind of pigment, can enumerate pigment of pigment such as black, yellow, orange, brown, redness, purple, cyan, green, fluorescent pigment, metal powder pigment, other pigment polymer combinations etc.The details of these pigment is opened narration to some extent in paragraph [0052]～[0054] in the flat 10-39509 communique the spy, and these also all are suitable for the present invention.In the middle of these pigment, preferred carbon black.

In photosensitive layer, total solids content with respect to photosensitive layer, the content of above-mentioned dyestuff or pigment is preferably 0.01～50wt%, 0.1～10wt% more preferably, particularly under the situation of using dyestuff, most preferably be 0.5～10wt%, under the situation of using pigment, most preferably be 1.0～10wt%.

When above-mentioned content during less than 0.01wt%, speed is too low, when surpassing 50wt%, during as the offset printing plate originals, can pollute the problem of non-imaging moiety.

(B) compound of generation free radical

As producing the compound that is fit to the free radical of use in the present invention, can enumerate salt, be salt compounded of iodine, diazol, sulfonium salt etc. particularly.These salt have the function of acid-producing agent, when using with following radical polymerization type compound, the function as free radical polymerization initiator are arranged.Fit for service salt is the middle salt of representing of general formula (III)～(V) as described below in the present invention.

General formula (III)

General formula (IV)

General formula (V)

In general formula (III), Ar ¹¹And Ar ¹²Expression preferably has the alkyl of substituent carbon number below 20 independently of one another.These alkyl preferably have substituting group, as substituting group can enumerate halogen atom, nitro, carbon number less than 12 alkyl, carbon number less than 12 alkoxyl or carbon number less than 12 aryloxy group.Z ^11-Expression is selected from halide ion, crosses the antithesis ion of chlorate ions, tetrafluoro boric acid ion, hexafluorophosphoric acid ion and azochlorosulfonate acid ion, preferred chlorate ions, tetrafluoro boric acid ion and the hexafluorophosphoric acid ion crossed.

In general formula (IV), Ar ²¹Expression preferably has substituent carbon number less than 20 aryl.As preferred substituted can enumerate halogen atom, nitro, carbon number less than 12 alkyl, carbon number less than 12 alkoxyl, carbon number less than 12 aryloxy group, carbon number less than 12 alkyl amino, carbon number less than 12 dialkyl amido, carbon number less than 12 arylamino or carbon number less than ammonia diaryl base of 12 etc.Z ^21-Expression and Z ^11-Antithesis ion with same meaning.

In general formula (V), R ³¹, R ³²And R ³³Respectively identical or different, expression preferably has substituent carbon number less than 20 alkyl.As preferred substituted, can enumerate halogen atom, nitro, carbon number less than 12 alkyl, carbon number less than 12 alkoxyl or carbon number less than 12 aryloxy group.Z ^31-Expression and Z ^11-The antithesis ion of same meaning.

As the object lesson of the salt that is suitable for, can enumerate the spy and be willing to the compound described in paragraph [0030]～[0033] in the flat 11-310623 specification in the present invention.

The salt of Shi Yonging in the present invention, maximum absorption wavelength is preferably below 400nm, below 360nm.Such absorbing wavelength is in the ultraviolet range, so the operation of offset printing plate originals can be carried out under incandescent lamp.

Such salt, with respect to the total solids content of photosensitive layer coating liquid, preferably with the ratio of 0.1～50wt%, more preferably with the ratio of 0.5～30wt%, especially preferably add in the photosensitive layer coating liquid with the ratio of 1～2wt%.If addition is less than 0.1wt%, speed is too low, when surpassing 50wt%, during as the offset printing plate originals, can pollute the problem of non-imaging moiety.Such salt is only used a kind of also passable, and is two or more and with also passable.These salt can add to in one deck with other composition, and the layer that other sets adds also passable.

(C) radical polymerization type compound

The radical polymerization type compound that uses in photosensitive layer of the present invention is the radical polymerization type compound with at least one ethene unsaturated double-bond, is selected to have at least one, the compound of preferred two unsaturated end group ethene.Such compound group is well-known in this technical field, and is also without particular limitation to this in the present invention.They have such as monomer, prepolymer, are forms such as dimer, tripolymer or oligomer, or their mixture and copolymer.Example as monomer and copolymer, unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid) and ester class, amide-type etc. are arranged, preferably use the ester, unsaturated carboxylic acid of unsaturated carboxylic acid and aliphatic polyol and acid amides that aliphatic polyamine forms etc.Also be suitable for using have hydroxyl, the substituent esters of unsaturated carboxylic acids of nucleophilicity, amide-type and simple function such as amino, sulfydryl or polyfunctional isocyanate's class, with the addition reaction of epoxies and the product of simple function or polyfunctional carboxylic acids dehydrating condensation etc.And have the addition reaction of the esters of unsaturated carboxylic acids of electrophilic groups such as NCO and epoxy radicals or amide-type and simple function or multifunctional alcohols, amine and thio-alcohol, the substituted reactant that particularly has the substituent esters of unsaturated carboxylic acids of detachment such as halogen group or tosyl or amide-type and simple function or polyfunctional alcohol, amide-type or a thio-alcohol also is fit to.And, replace above-mentioned unsaturated carboxylic acid can use the compound group of displacements such as unsaturated sulfonic acid, styrene as other example.

Radical polymerization type compound as the ester of aliphatic polyol and unsaturated carboxylic acid, the object lesson of acrylate, methacrylate, itaconate, crotonates, iso-crotonic acid ester, maleate, be willing in flat 11-310623 paragraphs [0037]～[0042] detailed narration is arranged the spy, these also are suitable for the present invention.

As the example of other ester, such as opening the aliphatic alkyl ester described in the clear 57-196231 communique the public clear 46-27926 communique of spy, special public clear 51-47334 communique, spy and opening the spy that clear 59-5240 communique, spy are opened clear 59-5241 communique, the spy opens the compound with aromatic series skeleton, the spy described in the flat 2-226149 communique and opens the amino compound that has described in the flat 1-165613 communique.

And as the object lesson of the amide monomer of aliphatic polyamine and unsaturated carboxylic acid, methylene diacrylamine, methylene DMAA, 1 are arranged, 6-hexa-methylene diacrylamine, 1,6-hexa-methylene DMAA, diethylenetriamines three acrylamides, xylylene diacrylamine, xylylene DMAA etc.

Preferred amide as other is the example of monomer, can enumerate at the compound with cyclohexylidene described in the public clear 54-21726 communique of spy.

The polyurethane series polyaddition type compound that carries out the addition reaction manufacturing with isocyanates and hydroxyl also is suitable, as such object lesson, can enumerate such as the addition on the polyisocyanate compounds that has 2 above NCOs on the molecule described in the public clear 48-41708 communique of spy the vinyl monomer that contains hydroxyl shown in the general formula as described below (VI), the vinyl urethane compound that in a molecule, contains the aggretion type vinyl more than 2 that obtains etc.

General formula (VI)

CH ₂＝C(R ⁴¹)COOCH ₂CH(R ⁴²)OH

(R here ⁴¹And R ⁴²Expression H or CH ₃)

It also is suitable that the spy opens the urethanes with oxirane pastern bone frame described in the urethane acrylate class described in clear 51-37193 communique, special fair 2-32293 communique, the special fair 2-16765 communique and special public clear 58-49860 communique, special public clear 56-17654 communique, special public clear 62-39417 communique, the special public clear 62-39418 communique.

And as open the spy that clear 63-277653 communique, spy are opened clear 63-260909 communique, the spy opens the radical polymerization type compound that has amino structure or sulfide structure described in the flat 1-105238 communique in molecule and also is fine.

As other example, can be the polyfunctional acrylic ester or the methacrylate of described polyester acrylate classes, epoxy resin and the reaction of (methyl) acrylic acid obtain in the middle of the spy opens clear 48-64183 communique, special public clear 49-43191 communique, special public clear 52-30490 communique etc. epoxy acrylate class etc.And, perhaps open vinyl phosphonate based compound described in the flat 2-25493 communique etc. and also be fine the spy at the specific unsaturated compound described in the public clear 46-43946 communique of spy, special fair 1-40337 communique, the special fair 1-40336 communique.In some cases, be suitable for using and contain the structure of opening the perfluoroalkyl described in the clear 61-22048 communique the spy.Also can use especially at " Japan's meeting will ", 20 volumes, No.7, p.300～308 the hardening monomer and the oligomer of (1984) middle introductions.

Which type of structure relevant these radical polymerization type compounds use, and use separately still to merge and use, the amount of adding how, and the details of using method, all will be in conjunction with the performance design of final entry material, suitably choice structure, prescription and addition.Implement the layer structure that be coated with or be coated with down on being and the method for coating according to different situations.

(D) bonding polymer

In the present invention, also to use bonding polymer.Preferably use linear organic polymer as bonding polymer.As such " linear organic polymer " and do not mind use any.Owing to preferably can carry out water video picture or the video picture of weak base water, be chosen in the linear organic polymer of solvable or swelling in water or the weak base water.Linear organic polymer is not only the epithelium that forms photosensitive layer and forms agent, and extensive selection is used for the developer as water, weak base water or organic solvent.Such as, just can carry out the water video picture with water-soluble organic polymer.As this linear organic polymer, the free radical polymer that has hydroxy-acid group on side chain is arranged, open such as out clear 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, spy the spy that clear 54-92723 communique, spy are opened clear 59-53836 communique, the spy opens the polymer described in the clear 59-71048 communique, i.e. the maleic acid of methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid, partial esterification etc.The same acid cellulose derivative that on side chain, has hydroxy-acid group in addition.In addition, have addition on the polymer of hydroxyl the polymer that obtains of cyclic acid anhydride also be useful.

Particularly therein, have (methyl) acrylic resin of benzyl or aryl and carboxyl on side chain, the balance of its film-strength, speed, video picture is all very excellent, is specially suitable.

Open clear 63-287947 communique, spy and open flat 1-271741 communique, specially be willing to the described polyurethane series bonding polymer that contains acidic group in the middle of the flat 10-116232 communique etc. and open clear 63-287944 communique, spy the fair 7-12004 communique of spy, special fair 7-120041 communique, special fair 7-120042 communique, special fair 8-12424 communique, spy, intensity is very excellent, all is being favourable part aspect anti-brush and the low exposure adaptability.

As other water soluble linear organic polymer, PVP or PEO etc. all is useful.And for improve the sclerosis epithelium intensity, alcohol soluble nylon or 2, the polyethers of 2-two-(4-hydroxyphenyl) propane and epoxychloropropane etc. also is useful.

The weight average molecular weight of the polymer that the present invention uses is preferably 10,000～300,000 especially preferably more than 5,000, and number-average molecular weight is preferably more than 1,000, the scope particularly preferably in 2,000～250,000.Polydispersity (weight-average molecular weight/number-average molecular weight) is preferably more than 1, in 1.1～10 scope.

Such polymer can be any in atactic polymer, block polymer, the graft polymers etc., preferably atactic polymer.

The polymer of Shi Yonging can synthesize with the past known method in the present invention.As the solvent that when synthetic, uses, can enumerate such as oxolane, dichloroethanes, cyclohexane, MEK, acetone, methyl alcohol, ethanol, glycol monoethyl ether, ethylene glycol monoethyl ether, acetate 2-methoxyl group ethyl ester, diethylene glycol dimethyl ether, 1-methoxyl group-2-propyl alcohol, acetate 1-methoxyl group-2-propyl ester, N, dinethylformamide, N, N-dimethylacetylamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide (DMSO), water etc.These solvents may be used alone, or two or more mixed.

The free radical polymerization initiator that uses when the polymer that synthetic the present invention uses can use known compounds such as the initator, peroxide initiator of azo system.

The bonding polymer of Shi Yonging can use separately in the present invention, or mixes and use.These polymer, with respect to photosensitive layer coating liquid total solids content 20～95wt%, the ratio of preferred 30～90wt% is added in the photosensitive layer.Addition is during less than 20wt%, when forming image, and the insufficient strength of image part.And addition can not form image when surpassing 95wt%.Weight ratio with the compound of the ethene unsaturated double-bond that can carry out radical polymerization and linear organic polymer is preferably in 1/9～7/3 scope.

The following describes the constituent of sour cross-linked layer.Infrared absorbent can use the identical material of (A) infrared absorbent that photopolymerization layer is described in front as used herein.

With respect to the total solids content of photosensitive layer, its preferred content is 0.01～50wt%, and more preferably 0.1～10wt% under the situation of dyestuff, most preferably is 0.5～10wt% especially, and under the situation of using pigment, most preferably is 1.0～10wt%.

If above-mentioned content is less than 0.01wt%, speed is very low, and when surpassing 50wt%, when using as the offset printing plate originals, can pollute non-imaging moiety.

(E) acid-producing agent

In embodiments of the invention, the acidic acid-producing agent of thermal decomposition exactly can acidic compound more than 100 ℃ by penetrating in the illumination of 200～500nm wavelength down or being heated to.

As above-mentioned acid-producing agent, can enumerate the light trigger of light cationic polymerization, the light trigger of photoionization base polymerization, light depigmenting agent, the phototropic agent of pigment or the known acid-producing agent that in little resist, uses etc., the acidic known compound of thermal decomposition and the mixture between them etc.

Such as in " photographic science engineering " (Photogr.Sci.Eng.) by S.I.Schlesinger, 18,387 (1974), people such as T.S.Bal at " polymer " (Polymer), diazol described in 21,423 (1980), United States Patent (USP) 4,069, No. 055 specification, ammonium salt described in the Te Kaiping 4-365049 communique, United States Patent (USP) 4,069,055,4, De phosphonium salt described in 069,056 specification such as grade, European patent 104,143, United States Patent (USP) 339,049,410,201 wait each specification, Te Kaiping 2-150848 communique, salt compounded of iodine described in the Te Kaiping 2-296514 communique, European patent 370,693,390,214,233,567,297,443,297,442, United States Patent (USP) 4,933,377,161,811,410,201,339,049,4,760,013,4,734,444,2,833,827, Deutsche Bundespatent 2,904,626,3,604,580,3,604,581 wait the sulfonium salt described in each specification.

Can enumerate people such as J.V.Crivello (Macromolecules) at " big molecule "; 10 (6); 1307 (1977); people such as J.V.Crivello are in " polymer science; the polymer chemistry volume " (Polymer Sci.Polymer Chem.Ed.); 17; selenium salt described in 1047 (1979); people such as C.S.Wen are at Teh; Proc.Conf.Rad.Curing ASIA; p.478; Tokyo; salt such as Arsenic salt described in October (1988); United States Patent (USP) 3905815 specifications; special public clear 46-4605 communique; the spy opens clear 48-36281 communique; the spy opens clear 55-32070 communique; the spy opens clear 60-239736 communique; the spy opens clear 61-169835 communique; the spy opens clear 61-169837 communique; the spy opens clear 62-58241 communique; the spy opens clear 62-212401 communique; the spy opens clear 63-70243 communique; the spy opens the organohalogen compound described in the clear 63-298339 communique; organic metal/organohalogen compound described in the Te Kaiping 2-161445 communique; European patent 0; 290; 750; 046; 083; 156; 535; 271; 851; 0; 388; 343; United States Patent (USP) 3; 901; 710; 4; 181; No. 531 each specifications; the spy opens clear 60-198538 communique; the spy opens the light acid propellant with o-nitrobenzyl base class blocking group described in the clear 53-133022 communique; European patent 0; 199; 672; 84515; 199; 672; 044; 115; 0; 101; 122; United States Patent (USP) 4; 618; 564; 4; 371; 605; 4; 431,774 each specification; the spy opens clear 64-18143 communique; Te Kaiping 2-245756 communique; imino group sulfonate described in the Te Kaiping 4-365048 communique is that the light of representative decomposes the compound that produces sulfonic acid; the spy opens the disulfo compound described in the clear 61-166544 communique.

Can also suitably enumerate these acidic groups or compound are imported the main chain of polymer or the compound of side chain, open clear 63-26653 communique, spy United States Patent (USP) 3849137, Deutsche Bundespatent 3914407 each specification, spy and open clear 55-164824 communique, spy and open clear 62-69263 communique, spy and open clear 63-146037 communique, spy and open that clear 63-163452 communique, spy are opened clear 62-153853 communique, the spy opens the compound described in the clear 63-146029 communique such as enumerating.

Also can use V.N.R.Pillai " synthesizing " (Synthesis), (1), 1 (1980), people such as A.Abad people such as " tetrahedron communication " (Tetrahedron Lett.) (47) 4555 (1971) .D.H.R.Barton at " chemical association magazine " (J.Chem.Soc.) (B), 329 (1970), United States Patent (USP) 3,779,778, the acidic compound of light described in European patent 126,712 each specification.

In the middle of the above-mentioned acid-producing agent, preferably use the compound of following general formula (I)～(V) expression:

Ar ¹-SO ₂-SO ₂-Ar ² (IV)

In above-mentioned general formula (I)～(V), R ¹, R ², R ⁴And R ⁵Can be identical or different, expression preferably has substituent carbon number less than 20 alkyl, R ³Expression preferably has halogen atom, substituent carbon number less than 10 alkyl, and perhaps carbon number is less than 10 alkoxyl.Ar ¹And Ar ²Can be identical or different, expression preferably has substituent carbon number less than 20 alkyl.R ⁶Expression preferably has substituent carbon number less than 20 divalent alkyl.N represents 0～4 integer.

In following formula, R ¹, R ², R ⁴And R ⁵The alkyl of carbon number 1～14 preferably.

The preferred embodiment of the acid-producing agent of above-mentioned general formula (I)～(V) expression is willing in flat 11-320997 paragraphs [0197]-[0222] detailed narration is arranged the inventor's spy.These compounds can be used in the spy and open flat 2-100054 communique, spy to open the method described in the flat 2-100055 communique synthetic.

Can enumerate salt as acid-producing agent (E), wherein can suitably enumerate compound with salt compounded of iodine, sulfonium salt, diazol structural formula with following general formula (VI)～(VIII) expression as halide or sulfonic acid antithesis ion.

Ar ³-I ⁺-Ar ⁴X ^-General formula (VI)

General formula (VII)

Ar ³-N ₂ ⁺X ^-General formula (VIII)

In above-mentioned general formula (VI)～(VIII), X represents halide ion, CIO ₄ ^-, PF ₆ ^-, SbF ₆ ^-, BF ₄ ^-Perhaps R ₇SO ₃ ^-, R here ⁷Expression preferably has substituent carbon number less than 20 alkyl.Ar ³And Ar ⁴Expression independently of one another preferably has substituent carbon number less than 20 aryl.R ⁸, R ⁹And R ¹⁰Expression preferably has substituent carbon number less than 18 alkyl.

In opening paragraph [0010]～[0035] of flat 10-39509 communique, the spy narrated this salt of general formula (I)～(III).

With respect to the total solids content of recording layer, the addition of acid-producing agent is preferably 0.01～50wt%, and more preferably 0.1～25wt% most preferably is 0.5～20wt%.

If less than above-mentioned addition, can not obtain image, and surpass 50wt%, during as the offset printing plate originals, the pollution of non-image part can take place when printing.

Above-mentioned acid-producing agent may be used alone, two or more kinds can also be used in combination.

(F) crosslinking agent

The following describes crosslinking agent, can enumerate following compound as crosslinking agent.

(i) aromatic compound that replaces with methylol or alkoxy methyl;

The compound that (ii) has N-methylol, N-alkoxy methyl or N-acyloxy methyl;

(iii) epoxide.

Be described in detail the compound of front (i)～(iii) below.

As the aromatic compound with methylol or alkoxy methyl replacement of above-mentioned (i), can enumerate such as using methylol, acetoxy-methyl or polysubstituted aromatic compound of alkoxy methyl or heterocyclic compound.But also comprise the known resin-like compound that obtains as the condensation under alkali condition by phenol and formaldehyde of phenolic resins.

In the middle of methylol or polysubstituted aromatic series of alkoxy methyl or heterocyclic compound, preferably with the hydroxyl position adjacent on have the compound of methylol or alkoxy methyl.

Carrying out with alkoxy methyl in the middle of polysubstituted aromatic series or the heterocyclic compound, the carbon number of preferred alkoxy methyl is less than 18 compound, the compound of more preferably following general formula (1)～(4) expression.

General formula (1)

General formula (2)

General formula (3)

General formula (4)

In above-mentioned general formula (1)～(4), L ₁～L ₈Represent methylol or alkoxy methyl that methoxy, ethoxyl methyl etc. replace less than 18 alkoxyl with carbon numbers independently of one another.

The advantage of such crosslinking agent is the cross-linking efficiency height, can improves anti-brush etc.

(ii) as compound with N-methylol, N-alkoxy methyl or N-acyloxy methyl, can enumerate European patent and disclose (being called EP-A below) 0,133,216, DRP 3,634, and 671,3,711, the compound that alkoxyl described in monomer described in 264 and oligomer-melamine-formaldehyde condensation products and urea-formaldehyde condensation products, EP-A 0,212,482 specifications replaces etc.

Wherein preferred such as the carbamide derivative with at least two free N-methylols, N-alkoxy methyl or N-acyloxy methyl, most preferably N-(alkoxymethyl)-2 radical derivative.

(iii) as epoxide, can enumerate the epoxide of monomer with an above epoxide group, dimer, oligomer, polymer shape, such as reaction product of the reaction product of enumerating bisphenol-A and epoxychloropropane, pf resin of low molecular weight and epoxychloropropane etc.

In addition, can enumerate 705, described in BP 1,539,192 each specification and the epoxy resin that uses at United States Patent (USP) 4,026.As crosslinking agent, state in the use under the situation of (i)～(iii) compound, with respect to the total solids content of photosensitive layer, its addition is preferably 5～80wt%, and more preferably 10～75wt% most preferably is 20～70wt%.

Under the situation less than above-mentioned addition, the photosensitive layer durability of the image recording material that obtains is low, and when surpassing 80wt%, the stability decreases during preservation.

In the present invention, as crosslinking agent, it also is suitable (iv) using the phenol derivatives of following general formula (5) expression.

At this, n and m are the integers greater than 1, and n is preferably 1～6, and m is excellent to be 1～10.

General formula (5)

In above-mentioned general formula (5), Ar ¹Expression has substituent aromatic hydrocarbon ring.

From the easy angle that obtains of raw material, as above-mentioned aromatic hydrocarbon ring, preferred phenyl ring, naphthalene nucleus or anthracene nucleus.And as their substituting group, preferred halogen atom, carbon number less than 12 alkyl, carbon number less than 12 alkoxyl, carbon number less than 12 alkylthio group, cyano group, nitro, trifluoromethyl etc.

In the middle of above-claimed cpd, from having the angle of ISO, as Ar ¹Preferably do not have substituent phenyl ring, naphthalene nucleus, in other words conj.or perhaps have halogen atom, carbon number less than 6 alkyl, carbon number less than 6 alkoxyl, carbon number less than substituent phenyl ring or naphthalene nucleus such as 6 alkylthio group or nitros.

(G) buck soluble high-molecular compound

As the buck soluble compound of the operable crosslinking agent of the present invention, can enumerate lacquer resin or on side chain, have polymer of hydroxyaryl etc.As above-mentioned lacquer resin, can enumerate the product of phenol and formaldehyde condensation under acid condition.

Therein, preferably such as the lacquer resin that obtains by phenol and formaldehyde, the lacquer resin that obtains by m-cresols and formaldehyde, the lacquer resin that obtains by p-cresols and formaldehyde, the lacquer resin that obtains by o-cresols and formaldehyde, the lacquer resin that obtains by octyl phenol and formaldehyde, by mixing the lacquer resin that m-/p-cresols and formaldehyde obtain, by phenol/cresols (m-, p-, o-, perhaps m-/p-, m-/o-, the any mixing of o-/p-can) mixture and the lacquer resin that obtains of formaldehyde, be raw material perhaps with phenol and paraformaldehyde, do not use catalyst, the ortho position that reaction obtains under airtight high pressure is in conjunction with the high HMW lacquer resin of rate.

Above-mentioned lacquer resin can be 800～300000 by its weight average molecular weight, and number-average molecular weight is in 400～0000, selects suitable product according to purpose.

And the polymer that has hydroxyaryl on above-mentioned side chain also is preferred, as the hydroxyaryl in this polymer, can enumerate the aryl that combines an above hydroxyl.

As above-mentioned aryl, can enumerate phenyl, naphthyl, anthryl, phenanthryl etc., wherein from the angle of easy acquisition and rerum natura, preferred phenyl or naphthyl.

As the form that present embodiment may use, the polymer that has hydroxyaryl on side chain can be enumerated any one polymer of the construction unit that contains following described general formula (IX)～(XII) expression.But be not limited to these polymer in the present invention.

In general formula (IX)～(XII), R ¹¹Expression hydrogen atom or methyl.R ¹²And R ¹³Identical or different, expression hydrogen atom, halogen atom, carbon number less than 10 alkyl, carbon number less than 10 alkoxyl or carbon number less than 10 aryloxy group.Or R ¹²And R ¹³In conjunction with the phenyl ring or the cyclohexane ring that form condensation.R ¹⁴Expression singly-bound or carbon number are less than 20 bivalent hydrocarbon radical.R ¹⁵Expression singly-bound or carbon number are less than 20 bivalent hydrocarbon radical.R ¹⁶Expression singly-bound or carbon number are less than 10 bivalent hydrocarbon radical.X ¹Expression singly-bound, ehter bond, thioether bond, ester bond or amido link.P represents 1～4 integer, and q and r represent 0～3 integer independently of one another.

As such alkali-soluble macromolecule, in the spy who is proposed by the inventor is willing to paragraph [0130]～[0163] of flat 11-320997 specification, detailed narration is arranged.

Operable buck solubleness high molecular compound in the form of this enforcement can only use a kind ofly, also can be used in combination of two or more.

With respect to the total solids content of photosensitive layer, the addition of buck solubleness high molecular compound is preferably 5～95wt%, and more preferably 10～95wt% most preferably is 20～90wt%.

If the addition of buck soluble resin is less than 5wt%, the durability of recording layer is very poor, and surpasses 95wt%, then can not form image.

The known recording materials that are suitable for as the present invention, can enumerate the spy open negative-type image recording material, the spy of containing phenol derivatives described in the flat 8-276558 communique open negative-type recording materials, the spy of containing diazenium compound described in the flat 7-306528 communique open described in the flat 10-203037 communique ring contain the unsaturated bond heterocycle polymer, utilize acidic catalyst to carry out the negative-type image recording material of cross-linking reaction, recording layer described here can be suitable for as the sour cross-linked layer of negative film photosensitive layer of the present invention.

(2) positive type photosensitive layer:

In positive type photosensitive layer, make as the disconnection of the key in the macromolecular compound of bonding agent by light or heat, remove the interaction between the macromolecule, improved the solubility that alkali is developed and distinguishes.As such bonding polymer, can enumerate on main chain in macromolecule and/or the side chain and contain single polymer of acidic-group, their copolymer or their mixture.

Wherein, have the polymer as the acidic-group of giving an example in following (1)～(6) on high molecular main chain and/or side chain, preferably solubility, the discovery to alkaline-based developer has dissolving to suppress each points such as energy.

(1) phenolic group (Ar-OH)

(2) sulfoamido (SO ₂NH-R)

(3) substituted sulfonamides base (being called " active amide base " below) [SO ₂NHCOR ,-SO ₂NHSO ₂R ,-CONHSO ₂R]

(4) carboxyl (CO ₂H)

(5) sulfonic group (SO ₃H)

(6) phosphate (OPO ₃H ₃)

In above-mentioned (1)～(6), Ar represents preferably to have substituent divalent aryl, and R represents preferably have substituent alkyl.

Have in the buck soluble high-molecular of the acidic-group of selecting by above-mentioned (1)～(6), the buck soluble high-molecular that preferably has (1) phenolic group, (2) sulfoamido and (3) active amide base, the buck soluble high-molecular that particularly has (1) phenolic group or (2) sulfoamido is from guaranteeing that fully the aspect such as solubility, development latitude, film-strength to alkaline-based developer is most preferred.

As by the buck soluble high-molecular of selecting in above-mentioned (1)～(6), can enumerate such as following polymer with acidic-group.

(1) as buck soluble high-molecular with phenolic group, can enumerate the condensation polymer of condensation polymer, m-/p-cresols and formaldehyde of condensation polymer, p-cresols and formaldehyde of condensation polymer, m-cresols and the formaldehyde of phenol and formaldehyde, the condensation polymer of lacquer resin such as the condensation polymer of phenol and cresols (m-, p-or m/p-mix can) mixture and formaldehyde and 1,2,3,-thrihydroxy-benzene and formaldehyde.Can enumerate the copolymer that the compound copolymerization that has phenolic group on side chain obtains especially.The copolymer that perhaps also can use the compound that on side chain, has phenolic group to carry out copolymerization.

As compound, can enumerate acrylamide, Methacrylamide, acrylate, methacrylate or hydroxy styrenes etc. with phenolic group with phenolic group.

The weight average molecular weight of buck soluble high-molecular is 5.0 * 10 ²-2.0 * 10 ⁴, number-average molecular weight is 2.0 * 10 ²-1.0 * 10 ⁴, then its image formation performance is good.And such macromolecule not only can use separately, also can be used in combination.When being used in combination, as at United States Patent (USP) 4,123, described in 279, can unite the condensation polymer that uses tert-butyl phenol and formaldehyde, as octyl phenol and formaldehyde condensation products, but have the condensation polymer of the alkyl of carbon number 3～8 as substituent phenol and formaldehyde.

(2) as buck soluble high-molecular, can enumerate such as having the polymer that constitutes as the main composition composition with original minimal structure unit on the compound of sulfoamido with sulfoamido.As above-mentioned compound, can enumerate the compound that in molecule, has each more than one sulfoamido that on nitrogen-atoms, combines at least one hydrogen atom and unsaturated group that can polymerization.The low molecular compound that wherein preferably has sulfonyl imino group acryloyl group, pi-allyl or hydroxyl, replacement or mono-substituted amino-sulfonyl or replacement in molecule can be enumerated the compound such as following general formula 1～5 expression.

General formula 1

General formula 2

General formula 3

General formula 4

General formula 5

[in the formula, X ¹, X ²Independently of one another expression-O-or-NR ²⁷-.R ²¹, R ²⁴Represent independently of one another hydrogen atom or-CH ₃R ²², R ²⁵, R ²⁹, R ³²And R ³⁶Expression independently of one another preferably has alkylidene, cycloalkyl, arlydene or the aryl alkylene of substituent carbon number 1～12.R ²³, R ²⁷And R ³³Represent hydrogen atom independently of one another, preferably have alkyl, cycloalkyl, aryl or the aralkyl of substituent carbon number 1-12.And R ²⁶, R ³⁷Expression independently of one another preferably has alkyl, cycloalkyl, aryl, the aralkyl of substituent carbon number 1～12.R ²⁸, R ³⁰And R ³⁴Represent independently of one another hydrogen atom or-CH ₃R ³¹, R ³⁵Represent singly-bound independently of one another or preferably have alkylidene, cycloalkylidene, arlydene or the aryl alkylene of substituent carbon number 1～12.Y ³, Y ⁴Represent independently of one another singly-bound or-CO-].

In the middle of the compound of representing with general formula 1～5; for positive type offset printing material of the present invention, particularly suitable be methacrylic acid m-amino-sulfonyl phenyl ester, N-(p-amino-sulfonyl phenyl) Methacrylamide, N-(p-amino-sulfonyl phenyl) acrylamide etc.

(3) as having the buck soluble high-molecular of active amide base, can enumerate such as on compound with active amide base with the polymer of original minimal structure unit as the main composition composition.As above-mentioned this compound, can enumerate the compound of representing with following structural formula that in molecule, has each more than one active amide base and unsaturated group that can polymerization.

Particularly, can suitably use N-(p-tosyl) Methacrylamide, N-(p-tosyl) acrylamide etc.

(4) as buck soluble high-molecular, can enumerate such as on the compound that in molecule, has each more than one carboxylic acid group and polymerisable unsaturated group, with the polymer of original minimal structure unit as the main composition composition with hydroxy-acid group.

(5) as having sulfonic buck soluble high-molecular, can enumerate such as on the compound that in molecule, has each more than one sulfonic group, polymerisable unsaturated group, with the polymer of original minimal structure unit as the main composition composition.

(6) as buck soluble high-molecular, can enumerate such as on the compound that in molecule, has each more than one phosphate and polymerisable unsaturated group, with the polymer of original minimal structure unit as the main composition composition with phosphate.

Be formed in positive type image and form the buck soluble high-molecular that uses in the material, has minimal structure unit by the acidic-group of selecting in above-mentioned (1)～(6), and unnecessary only be a specific kind, also can use two or more minimal structure unit, the polymer that perhaps two or more minimal structure unit copolymerization with different acidic-groups form with identical acidic-group.

Methods such as known graft copolymerization before the method for copolymerization can be used, block copolymerization, random copolymerization.

Above-mentioned copolymer has the content of the compound with acidic-group copolymerization in copolymer selected by (1)～(6) preferably more than 10mol%, more preferably more than 20mol%.During less than 10mol%, the tendency that can not fully improve the video picture degree is just arranged.

As operable infrared absorbent in positive type photosensitive layer, must interact with bonding polymer and produce erect image (unexposed portion inhibition development with particular functional group, exposed portion is disengaged, promoted development), in this, the compound of salt type structure is particularly preferred, particularly, in the middle of the infrared absorbent that can use under the situation of above-mentioned negative-type, preferred especially anthocyanidin, pyrroles's salt.About the details of anthocyanidin and pyrroles's salt as previously described.

Here, be willing to that the spy anionic infrared absorbent described in flat 10-237634 number can be fit to use.Such anionic infrared absorbent refers on the parent nucleus of substance absorption infrared ray pigment does not have cationic structural, and has the material of anion structure.

Such as, can enumerate (a-1) anionic metal complex; (a-2) anionic carbon black; (a-3) anionic phthalocyanine dye.

Infrared absorbent has the function that the infrared ray that will absorb changes heat into, at this moment, in the negative-type recording materials, produces acid or free radical by the heat that takes place, and causes crosslinked or polymerisation in photosensitive layer, owing to be solidified to form the image part; And in positive type recording materials, the material that produces heat or light owing to laser scanning causes chemical reaction, and the chain dissolving in the polymer increases the solubility of the developer solution of exposed portion, and being removed by development just becomes non-development part.

Such photosensitive layer also can merge the foregoing known additive of use as required.

In the method for the invention,, can be dissolved in the solvent that can dissolve various compositions, be coated on the aluminium alloy plate again containing the photosensitive composition of composition as mentioned above in order on support, to form photosensitive layer.Solvent as used herein can be used alone or as a mixture the spy and open clear 62-251739 communique, the spy opens the organic solvent described in the flat 6-242597 communique.

Photosensitive composition with the dissolving of the solids content of 2～50wt%, disperse, be coated on the support again and carry out drying.

The layer (photosensitive layer) of the photosensitive composition that is coated with on support, its coating weight is different with purposes, generally is preferably 0.3～4.0g/m in dried weight ²For good.Coating weight reduces, and the light exposure that obtains image reduces, but film strength reduces.Along with coating weight increases, must increase light exposure, the sensitization film strength increases, and such as when using as printed panel, just can access the printed panel that folder is counted height (anti-printing).

In photosensitive composition, in order to improve the quality of coating surface, can add surfactant, preferred fluorine-containing especially is surfactant.

When making lithographic plate, can be earlier on support the coating the inside by the photosensitive composition layer on lining or surface, also can be coated with both simultaneously.

The mode of photosensitive coated layer and condition can be utilized the mode and the condition of many known photosensitive coated layers.That is to say, use the method for spreading rod, the method for use extrusion type coating machine, the method for slip flange coating machine all to be fine.And the condition, the physical property of liquid of coating etc. can be selected according to all conditions such as the coating weight of photosensitive layer and the physical property of photosensitive composition.

Explain several method below.

What Fig. 6 showed is an example of the apparatus for coating of coating photosensitive composition of the present invention, in Fig. 6, and the 506th, wire bar or recessing bar (abbreviating " bar " below as) rotate with identical direction with the sheet of advancing continuously (aluminium alloy plate) 504.The 507th, support component, the whole length upper support at bar 506 prevents to produce deflection on bar 506, and has the function of supplying with the fluid supplier of coating fluid 503 on bar 506.

In other words, coating fluid 503 is supplied on the bar of rotation by the feed flow guiding groove that forms between supply opening of setting on the support component 507 of bar 508 and the baffle plate 509, is coated on then on the sheet 504 of guiding, forms and films 505.At this moment, the contact portion between sheet 504 and bar 506 is carried out the metering of coating fluid 503, only required coating weight is coated on the sheet 504, and flowing down with the coating fluid of supplying with again 503 of other forms the liquid 511 that is detained.Therefore, under normal situation, coating fluid 503 is coated with through being detained between liquid 511 and the sheet 504.Can think like this that via being detained liquid 511 when being applied to coating fluid 503 on the sheet 504 505 the surface property of filming is better than former.And because the transfer of coating fluid on sheet, bar 506 has the function of coating and the function that the First Astronautic Research Institute for Measurement and Test need be coated with liquid measure simultaneously, and the integral body of device is very compact, not only can effectively utilize the space, and carries out the setting and the operation of various conditions easily.

In this mode, coating weight is by the size of coating rod Surface Groove, and promptly winding line is controlled coating weight with the size of all lines on the wire bar, and the scope of coating weight does not have significant limitation, is generally 3～100ml/m ²

The diameter of coating rod is generally 3～20mm also without limits.The rotation direction of coating rod is identical with the direct of travel of sheet, on the contrary can, coating speed can be in the scope of 10～150m/min.

As other method, can use by the extrusion coated liquid of extrusion type impregnator, to deliver to by on the lining roller, the coating fluid that is formed on the support of advancing is built bridge, in the rear portion decompression that coating fluid is built bridge, or the method that is coated with in the front pressurization that coating fluid is built bridge.

This mode can be controlled at 10～500cm to the coating weight of coating fluid according to the situation of sheet and the size of fluid supplier end hole ³/ m ²Degree.

As the condition of coating fluid, preferably cutting off underspeed 1001/sec, be that to be preferably 20～50dyne/cm, proportion be 0.8～1.2 for well for 0.7～60cp, 0.7～100cp, surface tension at 100～100000 o'clock.

And be generally the degree of 0.1～0.5mm between the hole of sheet and fluid supplier.

The following describes dry mode and condition.

Dry mode has in the spy drives the drying device described in the flat 6-63487 communique and disposes transfer roller, will transport the arch type dryer of sheet by folding mode on roller, in the top and bottom of sheet, by the nozzle air supply, makes the mode of sheet with the drying of floating on one side; Perhaps do not use hot blast, at high temperature heat, carry out dry mode by radiant heat with various medium; Perhaps use various medium warm-up mills, the roller of heating is contacted with sheet by the heat of conduction carry out dry mode etc.

Be described in detail the mode of using hot blast below.

Fig. 7 is a schematic summary section of representing the example of traditional drying device that uses in the present invention.The aluminium flake 621 of advancing continuously on guide roller R and growing size is coated with the coating fluid that contains solvent by coated article 622, introduces first section dry section 623.Be provided with air supply opening 625 and exhaust outlet 626 at first section dry section 623.By 40～130 ℃ of air supply opening 625 supplying temperatures, the hot blast of dew point-5～15 ℃, carry out water conservancy diversion by deflector 629, the wind speed with 0.5～4m/sec on the coating epithelium surface that is formed by above-mentioned coating process on the aluminium flake 621 contacts, and will be discharged by exhaust outlet 626 after this coated film drying.Reach that the coating epithelium on the aluminium flake 621 is the mantle state near the outlet of first section dry section 623.Guide the long size aluminium flake 621 of advancing continuously by following guide roller R, entering second section dry section 624.Second section dry section 624 also is provided with air supply opening 627 and exhaust outlet 628.Air supply opening 627 supplying temperatures are 60～150 ℃, and the hot blast that dew point is 5～20 ℃ is blown out by slit-shaped nozzle 630, contact tempestuously with the wind speed of 5～15m/sec and the coating epithelium surface of aluminium flake 621.Make the solvent evaporation on the coating epithelium whereby, the coating epithelium is solidified, discharge by exhaust outlet 628 with the gas after the coating epithelium contacts.

As slit-shaped nozzle 630, the nozzle bore 0.2～8mm of front end usually at spacing 30～300mm, uses under the condition of the distance 5～200mm of nozzle and sheet.

The surface of aforesaid photosensitive layer, the vacuum tractive time when using the vacuum bakeout frame to process exposure in order to shorten, prevent to toast stain, felt mat preferably is set.Particularly, can enumerate the method for described felt mat in the middle of the spy opens clear 50-125805 communique, special public clear 57-6582 communique, special public clear 61-28986 communique etc., the method for the pressed powder heat fusing described in the special public clear 62-62337 communique etc.

In the inside of offset printing plate support obtained by the method for the present invention,, be necessary to lay the coating (back coating) that forms by organic polymer in order to prevent the damage of the photosensitive layer under the repetition situation.As organic polymer, can enumerate the vitrifying transition temperature at the saturated copolyester more than 20 ℃, phenolic resins, polyvinyl acetal resin and vinylidene chloride copolymer resins etc.

As each above-mentioned photosensitive layer, the structure of one deck only has been described, but be suitable for the photosensitive layer that method of the present invention obtains and be not limited to this, also can use known sandwich construction, such as 2 layers of photosensitive layer that obtains by physical development core layer and silver halide emulsion layer, the polymer layer that polyfunctional monomer and multifunctional bonding agent are formed, by silver halide and reducing agent form the layer, three layers the photosensitive layer that contains aerobic blocking layer, the layer that contains lacquer resin and naphthoquinones triazo-compound, two layers the photosensitive layer that contains silver halide layer, by absorption laser layer and oleophilic layer or any one deck of hydrophilic layer or two-layer two to three layers the photosensitive layer of forming etc. that laser irradiation is removed, can also be provided with the photosensitive layer that contains organic photoconductor etc.

Specify the present invention by embodiment below, but the present invention is not limited to these.

Embodiment 1

Use the device of Fig. 1 of the material manufacturing of above-mentioned JIS A1050 to carry out the mechanical surface roughening and handle (mechanical surface roughening treatment process).As the slurries grinding agent, use the silica sand of 20 weight portion average external volume particle diameters, the 132 μ m that in water, disperse, rotating speed 250rpm, extruding force 10Kw.The mechanical surface roughening is handled the average surface roughness (Ra of back aluminium alloy plate ₇₅) be 0.45 μ m.

Then, on device shown in Figure 2, use the caustic soda aqueous solution that this aluminium alloy plate is carried out caustic corrosion and handle (caustic corrosion treatment process).At this moment, the concentration of caustic soda keeps 15wt%, and temperature keeps 50 ℃, and aluminium alloy plate is carried out caustic corrosion, and etching extent is 5g/m ²

After this, wash, and go powder bed to handle with salpeter solution.

Again, on device shown in Figure 3, carry out the electrolytic surface roughening and handle (electrolytic surface roughening operation).As electrolyte, use the solution contain 1wt% nitric acid and 0.5wt% aluminium, the mean flow rate of electrolyte is 2000mm/sec, transverse flow speed be distributed in above-mentioned mean flow rate ± 20% in.The waveform of power supply uses square wave.As counter electrode, the total electric weight of anode is 50C/dm with carbon electrode ², the total electric weight of negative electrode equals 0.9 with the ratio r (the total electric weight of the total electric weight/anode of negative electrode) of the total electric weight of anode.

Then, on device shown in Figure 2, this aluminium alloy plate is carried out caustic corrosion handle (caustic corrosion treatment process (B)).Aqueous slkali is the soda lye of 10wt%, 45 ℃ of temperature, and it is 1.5g/m that the change processing time makes etching extent ²

Again, on device shown in Figure 4, carry out anodized (anodized operation).Electrolyte uses sulfuric acid solution (400g/l, proportion 1.12, electrical conductivity 0.7S/cm), 35 ℃ of the temperature of electrolyte, oxide scale film amount 3g/m ²Current density 10A/dm ², the mean flow rate 1000mm/sec of electrolyte, transverse flow speed be distributed in above-mentioned mean flow rate ± 30% in.

Each operation through above-mentioned just produces the support that plate printing plate is used.

The plate printing plate that obtains with support on the coating fluid that mixes by following composition of coating, make and have photosensitive layer (dry film thickness 2g/m ²) lithographic printing original.With such lithographic printing original expose, processing such as development, just reach lithographic plate.

-carbon black dispersion liquid 10g;

The hexafluorophosphate 0.5g of the condensation product of-4-diazo aniline and formaldehyde;

The free radical copolymer of-methacrylic acid, acrylic acid 2-hydroxy methacrylate, benzyl methacrylate, acrylonitrile (mol ratio 15: 30: 40: 15, weight average molecular weight 100,000) 5g;

-malic acid 0.05g;

(Minnesota Mining and Manufacturing Company makes-fluorine-containing surfactant, FC-430) 0.05g;

-1-methoxyl group-2-propyl alcohol 80g;

-methyl lactate 15g;

-water 5g.

Embodiment 2～9 and reference examples 1～9

Except the change as shown in table 1 of the treatment conditions of electrolytic surface roughening operation and anodized, make lithographic plate similarly to Example 1

Table 1

	Electrolytic surface roughening treatment conditions				The anodized condition
	Electrolytic surface roughening treatment conditions				The anodized condition			Total electric weight (the C/dm of anode ²)	Electrolyte mean flow rate (mm/sec)	Cross direction profiles (%)	r (-)	Electrolyte mean flow rate (mm/sec)	Cross direction profiles (%)	Current density (A/dm ²)
	Embodiment 1	50	2000	20	0.9	1000	30	Total electric weight (the C/dm of anode ²)	Electrolyte mean flow rate (mm/sec)	Cross direction profiles (%)	r (-)	Electrolyte mean flow rate (mm/sec)	Cross direction profiles (%)	Current density (A/dm ²)	10
Embodiment 2	Embodiment 1	50	2000	20	0.9	1000	30	150	2000	20	0.9	1000	30	10	10
Embodiment 2	Embodiment 3	450	2000	20	0.9	1000	30	150	2000	20	0.9	1000	30	10	10
Embodiment 4	Embodiment 3	450	2000	20	0.9	1000	30	800	2000	20	0.9	1000	30	10	10
Embodiment 4	Embodiment 5	150	500	20	0.9	1000	30	800	2000	20	0.9	1000	30	10	10
Embodiment 6	Embodiment 5	150	500	20	0.9	1000	30	150	4000	20	0.9	1000	30	10	10
Embodiment 6	Embodiment 7	150	2000	50	0.9	1000	30	150	4000	20	0.9	1000	30	10	10
Embodiment 8	Embodiment 7	150	2000	50	0.9	1000	30	150	2000	20	0.7	1000	30	10	10
Embodiment 8	Embodiment 9	150	2000	20	1.0	1000	30	150	2000	20	0.7	1000	30	10	10
Reference examples 1	Embodiment 9	150	2000	20	1.0	1000	30	40	2000	20	0.9	1000	30	10	10
Reference examples 1	Reference examples 2	900	2000	20	0.9	1000	30	40	2000	20	0.9	1000	30	10	10
Reference examples 3	Reference examples 2	900	2000	20	0.9	1000	30	150	400	20	0.9	1000	30	10	10
Reference examples 3	Reference examples 4	150	5000	20	0.9	1000	30	150	400	20	0.9	1000	30	10	10
Reference examples 5	Reference examples 4	150	5000	20	0.9	1000	30	150	2000	60	0.9	1000	30	10	10
Reference examples 5	Reference examples 6	150	2000	20	0.6	1000	30	150	2000	60	0.9	1000	30	10	10
Reference examples 7	Reference examples 6	150	2000	20	0.6	1000	30	150	2000	20	1.1	1000	30	10	10
Reference examples 7	Reference examples 8	150	2000	20	0.9	3000	30	150	2000	20	1.1	1000	30	10	10
Reference examples 9	Reference examples 8	150	2000	20	0.9	3000	30	150	2000	20	0.9	1000	60	10	10

The total electric weight of the total electric weight/anode of r=negative electrode

Speed (processing inhomogeneities) when the printability resistance of the plate printing plate of evaluation embodiment 1～9 and reference examples 1～9, contaminative and laser shine.Printability resistance is estimated with the printing number of printing machine (printing machine of the trade name Sorkz that the other Lu Gu of Hai Delu (Ha イデ Le ベ Le グ) company makes).Contaminative is that the center is estimated with the stain number on every.Speed during the laser irradiation is that can evaluation carry out the record of image when shining energy with the laser irradiation change of the about 830nm of wavelength.The result is as shown in the table 2.

The standard of estimating is as follows:

(1) about contaminative

Zero: non-image position is not fully by ink pollution;

*: non-image position is significantly by ink pollution.

(2) about handling inhomogeneities

Zero: do not handle inhomogeneous (surface quality inhomogeneous) fully;

*: it is inhomogeneous that surface quality takes place significantly.

Table 2

	Printability resistance (thousand sheets)	Contaminative	Handle inhomogeneous
	Printability resistance (thousand sheets)	Contaminative	Handle inhomogeneous	Embodiment 1	55	○	○
Embodiment 2	62	○	○	Embodiment 1	55	○	○
Embodiment 2	62	○	○	Embodiment 3	70	○	○
Embodiment 4	78	○	○	Embodiment 3	70	○	○
Embodiment 4	78	○	○	Embodiment 5	60	○	○
Embodiment 6	63	○	○	Embodiment 5	60	○	○
Embodiment 6	63	○	○	Embodiment 7	61	○	○
Embodiment 8	58	○	○	Embodiment 7	61	○	○
Embodiment 8	58	○	○	Embodiment 9	62	○	○
Reference examples 1	40	×	×	Embodiment 9	62	○	○
Reference examples 1	40	×	×	Reference examples 2	75	×	○
Reference examples 3	62	○	×	Reference examples 2	75	×	○
Reference examples 3	62	○	×	Reference examples 4	55	×	×
Reference examples 5	59	○	×	Reference examples 4	55	×	×
Reference examples 5	59	○	×	Reference examples 6	45	×	×
Reference examples 7	64	○	×	Reference examples 6	45	×	×
Reference examples 7	64	○	×	Reference examples 8	62	○	×
Reference examples 9	61	○	×	Reference examples 8	62	○	×

As can be seen from Table 2, to embodiment, the speed when printability resistance, contaminative and laser shine is all very good.Reference examples 1 and 2 and the poor adherence of photosensitive layer and support, printability resistance is not good.Pollute easily at reference examples 3 non-image positions, and the speed during laser irradiation simultaneously is low, needs very big energy when laser shines.Reference examples 4 and 5, inhomogeneous in the generation of the surface of support, the thickness of epithelium is also inhomogeneous, and reference examples 6 printability resistances are bad, and the electric current at reference examples 7 and 8 aluminium alloy plate edges is concentrated, and does not form goods.

Embodiment 10

Identical with embodiment 1, the mechanical surface roughening that carries out aluminium alloy plate is handled, caustic corrosion is handled, go powder bed to handle and the electrolytic surface roughening is handled.At this, when carrying out the processing of electrolytic surface roughening, the waveform trapezoidal wave of power supply, fluid temperature are 50 ℃.For alternating current, current value is 1msec by 0 time to peak value (Tp).The total electric weight of anode is 180C/dm ²

After the electrolytic surface roughening is handled, measure the not rate of corrosion of aluminium alloy plate, average trench diameter and gash depth.The results are shown in Table 3.

Rate of corrosion is not on the area S of the 100 μ m * 100 μ m at aluminium alloy plate, obtains the total projected area S ' of the pore part that forms with SEM on area S, by formula (1-S '/S) 100 calculate.

Average trench diameter is that the mean value that equivalent diameter is justified in the projection of the groove that exists the scope of 100 μ m * 100 μ m on the photo of being taken by SEM (1500 times) is obtained.

Gash depth is by obtaining in the scope of observing 100 μ m * 100 μ m on the photo of atomic force microscope (1500 times) shooting.

Then with embodiment 1 the same caustic corrosion processing and the anodized of carrying out.

Through above operation, produce support body for lithographic plate printing plate, this support body for lithographic plate printing plate is provided with the photosensitive layer the same with embodiment 1, produces original edition of lithographic printing plate, and such lithographic printing original is treated as lithographic plate through exposure, development etc.

Embodiment 11～18 and reference examples 10～18

In corrosion treatment operation (A) and the etching extent (B), the electrolytic surface roughening condition in the electrolytic surface roughening treatment process and average trench diameter, average gash depth, not rate of corrosion by the variation shown in the table 3 beyond, other is the same with embodiment 10, makes lithographic plate.

Table 3

	Etching extent (the g/m of (A) is handled in caustic corrosion ²)	Electrolytic surface roughening operation						Etching extent (the g/m of (B) is handled in caustic corrosion ²)
		Electrolytic surface roughening operation							Electrolyte temperature (℃)	Electrolyte flow rate (mm/sec)	Total electric weight (the C/dm of anode ²)	Average trench diameter (μ m)	Average gash depth (μ m)	Rate of corrosion (%) not
		Embodiment 10	5	65	2000	180	1.2		Electrolyte temperature (℃)	Electrolyte flow rate (mm/sec)	Total electric weight (the C/dm of anode ²)	Average trench diameter (μ m)	Average gash depth (μ m)	Rate of corrosion (%) not	0.55	0	1.0
Embodiment 11	5	Embodiment 10	5	65	2000	180	1.2	80	2000	100	0.6	0.25	0	0.1	0.55	0	1.0
Embodiment 11	5	Embodiment 12	5	90	2000	80	0.4	80	2000	100	0.6	0.25	0	0.1	0.1	0	0.05
Embodiment 13	5	Embodiment 12	5	90	2000	80	0.4	80	2000	100	0.6	0.25	30	0.1	0.1	0	0.05
Embodiment 13	5	Embodiment 14	5	80	2000	100	0.6	80	2000	100	0.6	0.25	30	0.1	0.25	15	0.1
Embodiment 15	5	Embodiment 14	5	80	2000	100	0.6	80	4000	100	0.6	0.25	0	0.1	0.25	15	0.1
Embodiment 15	5	Embodiment 16	5	80	2000	100	0.6	80	4000	100	0.6	0.25	0	0.1	0.25	0	0.1
Embodiment 17	1	Embodiment 16	5	80	2000	100	0.6	80	2000	100	0.6	0.25	0	0.1	0.25	0	0.1
Embodiment 17	1	Embodiment 18	20	80	2000	100	0.6	80	2000	100	0.6	0.25	0	0.1	0.25	0	0.1
Reference examples 10	5	Embodiment 18	20	80	2000	100	0.6	60	2000	180	1.4	0.55	0	1.0	0.25	0	0.1
Reference examples 10	5	Reference examples 11	5	95	2000	100	The groove dissolving	60	2000	180	1.4	0.55	0	1.0	The groove dissolving	0	0.05
Reference examples 12	5	Reference examples 11	5	95	2000	100	The groove dissolving	80	2000	100	0.6	0.25	40	0.1	The groove dissolving	0	0.05
Reference examples 12	5	Reference examples 13	5	80	400	100	0.6	80	2000	100	0.6	0.25	40	0.1	0.25	35	0.1
Reference examples 14	5	Reference examples 13	5	80	400	100	0.6	80	5000	100	0.6	0.25	35	0.1	0.25	35	0.1
Reference examples 14	5	Reference examples 15	0.5	80	2000	100	0.6	80	5000	100	0.6	0.25	35	0.1	0.25	0	0.1
Reference examples 16	25	Reference examples 15	0.5	80	2000	100	0.6	80	2000	100	0.6	0.25	0	0.1	0.25	0	0.1
Reference examples 16	25	Reference examples 17	5	65	2000	180	1.2	80	2000	100	0.6	0.25	0	0.1	0.65	0	0
Reference examples 18	5	Reference examples 17	5	65	2000	180	1.2	65	2000	180	1.2	0.3	0	1.2	0.65	0	0

The evaluation of speed (processing inhomogeneities) the results are shown in Table 4 when the plate printing plate of embodiment 10～18 and reference examples 10～18 carried out the printability resistance identical with embodiment 1, contaminative and laser irradiation.

Table 4

	Printability resistance (thousand sheets)	Contaminative	Handle inhomogeneities
	Printability resistance (thousand sheets)	Contaminative	Handle inhomogeneities	Embodiment 10	70	○△	○
Embodiment 11	67	○	○	Embodiment 10	70	○△	○
Embodiment 11	67	○	○	Embodiment 12	68	○	○
Embodiment 13	65	○△	○	Embodiment 12	68	○	○
Embodiment 13	65	○△	○	Embodiment 14	68	○	○
Embodiment 15	70	○	○	Embodiment 14	68	○	○
Embodiment 15	70	○	○	Embodiment 16	68	○	○
Embodiment 17	72	○△	○	Embodiment 16	68	○	○
Embodiment 17	72	○△	○	Embodiment 18	65	○	○
Reference examples 10	50	○△	○	Embodiment 18	65	○	○
Reference examples 10	50	○△	○	Reference examples 11	10	○	○
Reference examples 12	45	○△	○	Reference examples 11	10	○	○
Reference examples 12	45	○△	○	Reference examples 13	35	○	×
Reference examples 14	40	○	×	Reference examples 13	35	○	×
Reference examples 14	40	○	×	Reference examples 15	75	×	○
Reference examples 16	48	○	○	Reference examples 15	75	×	○
Reference examples 16	48	○	○	Reference examples 17	72	△×	○

Find out that by table 4 to embodiment, the speed when printability resistance, contaminative and laser shine is all fine.Reference examples 10 and 11, the poor adherence of photosensitive layer and support, printability resistance is not good.Pollute easily at the non-image position of reference examples 12, and the speed in laser when irradiation is low, during the laser irradiation very big energy must be arranged.Inhomogeneities takes place on the surface of support in reference examples 13 and 14, and the thickness of epithelium is also inhomogeneous.The printability resistance of reference examples 15 is poor, and reference examples 16 and 17 aluminium alloy plate marginal portion electric current are concentrated can not manufacture goods.

If according to method of the present invention, just can produce support body for lithographic plate printing plate with excellent in resistance printing, contaminative and surface quality.

Claims

1. the manufacture method of support body for lithographic plate printing plate, it is characterized in that, this method is a kind of manufacture method that comprises the plate printing plate of surface roughening treatment process and anodized operation with support, above-mentioned surface roughening treatment process comprises electrolytic surface roughening treatment process and caustic corrosion treatment process, in above-mentioned electrolytic surface roughening operation, the total electric weight of anode that the electrolytic surface roughening is handled is 50～800C/dm ²The electrolyte that uses when carrying out anodized in above-mentioned anodized operation contains sulfuric acid, respectively the temperature of electrolyte is controlled at 5～70 ℃ scope, the electrical conductivity of electrolyte is controlled at the scope of 0.1～0.9S/cm, the specific gravity control of electrolyte in 1.05～1.20 scope.

2. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1, it is characterized in that, wherein be included in caustic corrosion treatment process (A) and the caustic corrosion treatment process (B) after above-mentioned electrolytic surface roughening treatment process before the above-mentioned electrolytic surface roughening treatment process at least as above-mentioned caustic corrosion treatment process, handling the etching extent that causes by caustic corrosion in above-mentioned caustic corrosion treatment process (A) is 1～20g/m ²In above-mentioned electrolytic surface roughening treatment process, handle the not rate of corrosion forms below 30% by the electrolytic surface roughening, the average diameter of the groove of formation is 0.1～1.2 μ m, on average gash depth is 0.05～0.6 μ m; Handling the etching extent that forms by caustic corrosion in above-mentioned caustic corrosion treatment process (B) is 0.01～1.0g/m ²

3. as the manufacture method of the support body for lithographic plate printing plate of claim 1 or 2, it is characterized in that in above-mentioned electrolytic surface roughening treatment process, the rate of circulating flow that is used for the electrolyte that above-mentioned electrolytic surface roughening handles is 500～4000mm/sec.

4. the manufacture method of support body for lithographic plate printing plate as claimed in claim 3 is characterized in that, the transverse flow speed of the electrolyte that in above-mentioned electrolytic surface roughening is handled, uses be distributed in above-mentioned mean flow rate ± 50% in.

5. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1 is characterized in that, in above-mentioned anodized operation, the mean flow rate that is used for the electrolyte of anodized is 10～2500mm/sec.

6. the manufacture method of support body for lithographic plate printing plate as claimed in claim 5 is characterized in that, the transverse flow speed of the electrolyte that in above-mentioned anodized, uses be distributed in above-mentioned mean flow rate ± 50% in.

7. the manufacture method of support body for lithographic plate printing plate as claimed in claim 5 is characterized in that, the current density in above-mentioned anodized operation is 2～50A/dm ²

8. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1 or 2 is characterized in that, in above-mentioned electrolytic surface roughening operation, the ratio of total electric weight of negative electrode and the total electric weight of anode (the total electric weight of the total electric weight/anode of negative electrode) is 0.7～1.0.

9. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1 or 2 is characterized in that, in above-mentioned electrolytic surface roughening treatment process, the temperature of the electrolyte that the electrolytic surface roughening is handled is 65～90 ℃.

10. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1 is characterized in that, in above-mentioned electrolytic surface roughening treatment process, the rise time of electrolysis power AC wave shape, (Tp value) was below 2.0msec.

11. the manufacture method of support body for lithographic plate printing plate as claimed in claim 1 or 2 is characterized in that, in above-mentioned electrolytic surface roughening operation, the total electric weight of anode that is used for the processing of electrolytic surface roughening is 50～180C/dm ²