CN1192905C

CN1192905C - Method for making offset printing plate supporting body, affset printing plate supporting body and offset printing plate

Info

Publication number: CN1192905C
Application number: CN 01102333
Authority: CN
Inventors: 上杉彰男
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2000-02-04
Filing date: 2001-02-02
Publication date: 2005-03-16
Anticipated expiration: 2021-02-02
Also published as: CN1316338A; JP2001213066A

Abstract

To provide a manufacturing method for a lithographic printing plate support, by which a lithographic printing plate keeping a certain fixed quality and excellent in printing performances and printing plate performances can be supplied, the lithographic printing plate support manufactured by the manufacturing method, and the lithographic printing plate made from the lithographic printing plate support. By applying treatments of at least three processes among the following five processes (1) to (5) to the surface of an aluminum plate, a lithographic printing plate support having favorable physical surface properties is manufactured: a process (1) for a specified mechanical surface roughening, a process (2) for a specified etching, a process (3) for a specified electrochemical surface roughening, a process (4) for a specified anodic oxidizing film forming and a processes (5) for a specified treatment for obtaining hydrophilicity.

Description

The manufacture method of lithographic plate supporting mass, lithographic plate supporting mass and lithographic plate

Technical field

The invention relates to and adopt lithographic plate supporter that aluminium, aluminium alloy makes as the manufacture method of the lithographic plate supporter of supporter, by this manufacture method and the lithographic plate that adopts this lithographic plate supporter to make.

Background technology

As the used supporter of galley supporter, particularly lithographic plate, often adopt aluminium sheet or aluminium alloy plate etc.Generally speaking, to consider cohesiveness between it and photosensitive material and its water imbibition when using aluminium sheet, and require the surface, more require to keep the surface that suitable hardness and high traumatic resistance are arranged through uniform rugosityization as supporter.

Now, the lithographic printing development speed is very fast, and the lithographic plate that is adopted in the lithographic printing is widely used.How to set up large batch of lithographic plate production system and become important topic.In mass-produced system, how the good galley of quality bills of materials, how Min. ground reduces standard error also is very important problem.

In order to address the above problem, the spy opens and proposes defining of the capillary number that obtains to arithmetic average roughness, coating speed, viscosity and by surface tension in the flat 8-168719 communique, so that realize the more coating of high speed.

But aspect lithographic plate, can not only see the coating performance, its surface-treated stability is also very important, and the particularly production in enormous quantities under creating conditions at a high speed guarantees that the quality of lithographic plate also is very important.

Summary of the invention

At above problem, the purpose of this invention is to provide a kind of manufacture method of lithographic plate supporter, by the supporter of this method manufacturing and the lithographic plate that adopts this supporter to make, make this lithographic plate will possess certain quality, printing, brush version excellent performance.

For achieving the above object, the present invention takes following design:

＜1 〉, a kind of manufacture method of lithographic plate supporter, it is characterized in that: to surface of aluminum plate as supporter, the processing of at least three operations in operation (1)-(5) below implementing:

Operation (1): with the abrasive of proportion in central value ± 10% scope, surface of aluminum plate is carried out the mechanical asperities chemical industry preface of mechanicalness asperitiesization, described proportion central value is 1.05-1.95;

Operation (2): with NaOH is Main Ingredients and Appearance, with proportion in central value ± 10% scope, the aqueous slkali of electrical conductivity in central value ± 20% scope, the erosion operation of surface of aluminum plate being carried out etch, described proportion central value is 1.2-1.6, and described electrical conductivity central value is 0.15-0.4S/cm;

Operation (3): with hydrochloric acid or nitric acid is main component, with electrical conductivity in central value ± 20% scope, the electrolyte of ultrasonic velocity in central value ± 20% scope, surface of aluminum plate is carried out the electrochemistry asperities chemical industry preface of electrochemistry asperitiesization, described electrical conductivity central value is 10-300 (mS/cm), and described ultrasonic velocity central value is 1500-1600 (m/see);

Operation (4): with sulfuric acid is main component, with proportion in central value ± 10% scope, the electrolyte of electrical conductivity in central value ± 20% scope, the anode oxide film that surface of aluminum plate is generated oxide-film generates operation, described proportion central value is 1.05-1.20, and described electrical conductivity central value is 0.1-0.9 (S/cm);

Operation (5) is carried out the hydrophilicity-imparting treatment operation of hydrophilicity-imparting treatment with the electrolyte of electrical conductivity in the scope of central value ± 20% to surface of aluminum plate, and described electrical conductivity central value is 2-60 (mS/cm).

＜2〉with aforementioned＜1〉manufacture method of lithographic plate supporter, 1.～4. the physical property of resulting supporting body surface should satisfy following rerum natura:

Rerum natura is 1.: surperficial arithmetic average roughness (Ra), in mean value ± 20% scope;

Rerum natura is 2.: surface smoothness, in mean value ± 10% scope;

Rerum natura is 3.: with AFM (AFM, horizontal direction resolution ratio: 0.1 μ m, measurement range: 100 * 100 (μ m)) measure the surface, trying to achieve surface area by approximate line-of-sight course is a, when the top projected area was b, the value of specific area a/b was in mean value ± 20% scope;

Rerum natura is 4.: (AFM, horizontal direction resolution ratio: 1.9 μ m, measurement range: 240 * 240 (μ m)) measure the surface, gradient is in the ratio more than 30 °, in mean value ± 20% scope with AFM.

＜3〉aforementioned＜1〉in the manufacture method of lithographic plate supporter, described three operations implementing at least are: operation (1) or (3), operation (2) and operation (4).

＜4〉aforementioned＜1〉manufacture method of described lithographic plate supporter, in described operation (1)～(4), each operation is carried out once at least.

＜5〉aforementioned＜1〉manufacture method of described lithographic plate supporter, in described operation (2)～(5), each operation is carried out once at least.

＜6〉aforementioned＜1〉manufacture method of described lithographic plate supporter, in described operation (1)～(5), each operation is carried out once at least.

＜7〉with aforementioned＜1〉supporter made of the manufacture method of described lithographic plate supporter, to surface of aluminum plate, below implementing in operation (1)～(5), the processing of at least three operations:

Operation (1):, surface of aluminum plate is carried out the mechanical asperities chemical industry preface of mechanicalness asperitiesization with the abrasive of proportion in central value ± 10% scope;

Operation (2): with NaOH is Main Ingredients and Appearance, uses proportion in central value ± 10% scope, the aqueous slkali of electrical conductivity in central value ± 20% scope, the erosion operation of surface of aluminum plate being carried out etch;

Operation (3): with hydrochloric acid or nitric acid is main component, and in central value ± 20% scope, the electrolyte of ultrasonic velocity in central value ± 20% scope carries out the electrochemistry asperities chemical industry preface of electrochemistry asperitiesization to surface of aluminum plate with electrical conductivity;

Operation (4): with sulfuric acid is main component, uses proportion in central value ± 10% scope, the electrolyte of electrical conductivity in central value ± 20% scope, and the anode oxide film that surface of aluminum plate is generated oxide-film generates operation;

Operation (5): the hydrophilicity-imparting treatment operation of surface of aluminum plate being carried out hydrophilicity-imparting treatment with the solution of electrical conductivity in central value ± 20% scope.

＜8〉adopt aforementioned＜1〉lithographic plate of the supporter made of the manufacture method of lithographic plate supporter, to surface of aluminum plate, below implementing in operation (1)～(5), the processing of at least three operations:

Description of drawings

The present invention will be described in detail below in conjunction with accompanying drawing.

Fig. 1 is that schematic diagram is put in mechanical asperities makeup

Fig. 2 is the etching device schematic diagram

Fig. 3 is that schematic diagram is put in the makeup of electrochemistry asperities

Fig. 4 is an anodic oxidation film device schematic diagram

Fig. 5 a is that the coating drying nest provides photosensitive layer applying device schematic diagram

Fig. 5 b is that another coating drying nest provides photosensitive layer applying device schematic diagram

Fig. 6 is that the coating drying nest carries out dry device schematic diagram to photosensitive layer

The manufacture method of A, lithographic plate supporter

The invention relates to the manufacture method of lithographic plate supporter, for surface of aluminum plate, in aforesaid operation (1)～(5), to carry out the processing of three operations at least, its result can make and satisfy the 1. aforementioned～4. supporter of the excellence of surface mass character.

At first being the explanation about aluminium sheet in this method, next is about aforementioned operation (1)～(5) surface treatment procedure, and satisfies 1.～4. explanation of surface mass character.

[aluminium sheet]

Aluminium sheet that the present invention adopts comprises fine aluminium and aluminium alloy.Can use various metals in the aluminium alloy, as: silicon, copper, manganese, chromium, magnesium, zinc, nickel ... Deng alloy.

Aluminium alloy is used as concrete, can enumerate a lot, as: special public clear 58-6635 communique is pointed out aluminium alloy as the hectographic printing plate, employing be Fe, the Si that certain ingredients is arranged and the aluminium alloy of metallic compound.Special public clear 58-28874 communique has then proposed to carry out cold rolling, intermediate annealing, the aluminium alloy of the applied voltage method of usefulness electrolysis rugosityization etc.

And, at the public clear 62-41304 of spy number, special fair 1-46577 number, special fair 1-46578 number, special fair 1-47545 number, special fair 1-35910 number, special public clear 63-60823 number, special public clear 63-60824 number, special fair 4-13417 number, special fair 4-19290 number, special fair No. 19291, special fair 4-19293 number, special public clear 62-50540 number, the spy opens clear 61-272357 number, the spy opens clear 62-74060 number, the spy opens clear 61-201747 number, the spy opens clear 63-143234 number, the spy opens clear 63-143235 number, the spy opens clear 63-255338 number, Te Kaiping 1-283350 number each communique, EP272528 number, No. 4902353, United States Patent (USP), No. 3232810, West Germany's special permission, No. 435230, U.S.'s special permission, EP239995 number, No. 4822715, U.S.'s special permission, No. 3507402, West Germany's special permission, No. 4715903, U.S.'s special permission, No. 3507402, West Germany's special permission, EP289844 number, No. 5009722, U.S.'s special permission, with No. 4945004, No. 3714059, West Germany's special permission, No. 4686083, U.S.'s special permission, with No. 4861396, in EP158941 number each specification, also enumerated the example of aluminium alloy.Not only be confined to listed enumerating, general aluminium alloy can adopt fully.

The manufacture method of the aluminium sheet that the front is said has occurred the method for direct casting again in recent years except the hot rolling method.

For example in No. 252799, Deutsches Wirtschafts Patent, introduced the method for making sheet material with two rollers; EP223737 number, No. 4802935, United States Patent (USP), with in No. 4800950 the specification, hope can be fixed the microalloy composition; In the EP415238 specification, advise with direct casting and direct casting+hot rolling method.

Aforementioned aluminium sheet can carry out ungrease treatment according to different situations.Generally adopt following method when carrying out ungrease treatment:, perhaps use the alkali degreasing method of alkali etchants such as NaOH, KOH with the method for interfacial agent.

Problem aspect the spy opens the ungrease treatment of having put down in writing aluminium sheet among the flat 2-026793.

The solvent degreasing method is as adopting oil system solvents such as gasoline, kerosene, volatile oil, solvent naphtha, n-hexane; Adopt trichloro-ethylene, methene chloride, perchloroethylene, 1,1, chlorinated solvents such as 1-trichloroethanes.

Surfactant degreasing method adopts the activating agent of selling on the various markets such as the aqueous solution of anion, cation, nonionic surfactant or amphoteric surfactant.

The alkali degreasing method is as adopting NaOH, Na ₂CO ₃, NaHCO ₃, Na ₂SO ₄Method Deng the aqueous solution of sodium salt, or adopt the method for the aqueous solution of orthosilicate sodium, sodium metasilicate, No. 2 sodium metasilicate, No. 3 silicate such as sodium metasilicate and the method that adopts aqueous phosphatics such as sodium phosphate, sodium pyrophosphate, second sodium phosphate, sodium phosphate trimer, sodium tripolyphosphate, calgon.

When utilizing the alkali degreasing method, because of processing time, temperature problem might cause dissolving to surface of aluminum plate, therefore for ungrease treatment, these dissolution phenomenas do not wish to take place.

These degreasing methods can adopt infusion process, spraying process, contain the method for the wipings such as cloth of liquid, but also can and use with ultrasonic method.

Aforesaid aluminium sheet before the various surface treatments afterwards, wishes to grind in advance, and pre-abrasive method generally is electrochemistry and mechanical means.

Adopt electrochemical method to grind in advance, generally at H ₂SO ₄Dc electrolysis carries out in the liquid, this situation H ₂SO ₄Liquid concentration is in 15%～80% (weight), and temperature adopts direct current at 40～80 ℃, and current density is 5A/dm ²～50A/dm ², electric weight is 100～3000c/dm ²Be advisable.

On the other hand, utilize mechanical means to wish the nonwoven that adopts polyamide, polyester, artificial silk etc. to make, the roller of making of the grinding-material that comprises average grain diameter 1～25 μ m grinds.

It is grinding condition that selection can form certain surface roughness, and roller directly is 200～1000mm, for uniform surface is arranged, when when handling continuously with the vertical direction of the rolling direction of slab, preferably gives 5～2000 time/minute the vibration vertical with the line direction.In any case, for the surface of aluminium sheet, owing to grind, wish that obtaining arithmetic average roughness Ra is 0.15～0.35 μ m, reaching and forming maximum height Ry is 1～3.5 μ m, is promptly ground in advance by above-mentioned dc electrolysis or roller, and hope can obtain aforesaid Ra and Ry.

[surface treatment procedure]

The present invention makes lithographic plate supporter aspect, in above-mentioned operation (1)～(5), will implement the processing of three operations at least, below explanation respectively.

Operation (1): mechanical asperities chemical industry preface

For mechanical asperities chemical industry preface, the device (as shown in Figure 1) that can use special public clear 50-40047 communique to be put down in writing, in Fig. 1, when aluminium sheet 1 moves along the arrow A direction, abrasive body 3 is sent to aluminium sheet 1 surface, roll shape brush 2 with two and make surperficial asperitiesization, this brush 2 that carries out asperitiesization comprises nylon brush and brass wire brush.

And, in Fig. 1,, mechanical asperities is divided two sections carries out in order to carry out good asperitiesization.Among the present invention, the hop count of mechanical asperitiesization is not particularly limited, can more than one section or three sections and three sections.

To mechanical asperities method (the sand grains method of machinery), adducible have the ball of being called as polishing (grinding agent is arranged, steel ball or magnetic ball are rolled), hydro-abrasion air-flow spraying process, brush polishing thereon and with the slip injection method of water under high pressure on metallic plate.

The brush polishing will use according to actual needs.The feed liquid that is dispersed with grinding agent is placed on the processing plate, grind back and forth thereon with metal or resinous brush.Compare with additive method, it can be handled the metallic plate of web-like continuously with better simply equipment, is employed at print field recently that (as: ball grinds and just to be used in sheet material processing, and needs just can finish for a long time; The spraying polishing can carry out continuously, but not only needs huge equipment, and when printed panel is thin, the plane planarization is had very macrolesion.)。

But also there are several important problem in the brush polishing.

At first, run up, can cause the vibration of brush and processed plate, cause machined surface inhomogeneous in order to make brush.Particularly on instrument, because the brush wearing and tearing will be changed often and roll the shape brush.Therefore need to consider the charging crane of brush, normal like this causing brushed the destruction of rolling balance in the running in the mechanism, cause bigger vibration.Secondly, make the brush that rolls shape cause the problems such as directionality of abradant surface by the certain orientation running.

Undertaken asperitiesization by water under high pressure, open the spy that clear 59-21469 communique, spy are opened clear 60-19595 communique, the spy opens clear 60-18390 communique etc. once report.

The concentration of grinding-material is very big to the asperities influence in the abrasive body, and therefore, the concentration that regulate required grinding-material with certain density abrasive body is very important.Adjustable range is at central value ± 10%, in best ± 7%, if surpass ± 10%, then can produce the asperities degree and deviation occur because of the departing from of concentration, and causes the supporter that finally obtains, and then is the quality instability of lithographic plate.

All central values are meant that its occurrence is different because of the kind of grinding-material, kind, particle diameter and abradant brush, cannot treat different things as the same to the proportion of the suitable abrasive body of asperitiesization.General wish to be made as in 1.05～1.95 the scope, be preferably 1.10～1.25.

And, be provided with separators such as cyclonic separation in order to keep certain particle diameter, when untapped abrasive body is added, the abrasive body of fine grain is shifted out.

Operation (2): etch operation

So-called etch operation generally in order to make aluminium sheet smooth, even, is carried out chemically treated process with aqueous slkali to aluminium sheet.

Especially, when the back is talked about and is implemented electrochemistry asperities chemical industry preface and handle, if after asperities chemical industry preface, directly proceed, because of the asperitiesization uneven situation that becomes exists, so be effectively with the erosion operation.

Among the present invention, adopt the aqueous slkali based on NaOH, handle to obtain level and smooth etch face with the NaOH aqueous solution, not only quality is good, and price is also low.

Said at this is that the master is meant that as aqueous slkali composition NaOH be main with NaOH.Aqueous alkali among the present invention can be the mixed liquor of NaOH and other alkali composition, also can contain other micro constitutent.

Can enumerate with the composition that NaOH uses simultaneously, as Na ₂CO ₃, NaHCO ₃, Na ₂SO ₄Deng sodium salt, sodium metasilicate, sodium metasilicate, No. two sodium metasilicate, No. three silicate such as sodium metasilicate; Phosphate such as first sodium phosphate, sodium tripolyphosphate, second sodium phosphate, tripolyphosphate, sodium pyrophosphate, calgon.

Condition when etch is handled, NaOH concentration 0.01%～50% (weight) in the aqueous alkali, 20～90 ℃ of temperature, 5 seconds～5 minutes processing time, and the etch consumption is suitably selected according to the material and the desired quality of aluminium.

Open clear 54-65607 number, spy the spy and open in clear 55-125299 number each communique, studied the pre-treatment when electrified asperities processing.The spy opens clear 63-235500 number, spy and opens clear 63-307990 number, spy and open flat 1-127388 number, spy and open flat 1-160690 number, spy and open flat 1-136789 number, spy and open flat 1-136788 number, spy and open flat 1-178497 number, spy and open flat 1-308689 number, spy and open flat 3-126871 number, spy and open flat 3-126900 number, spy and each communique such as open flat No. 173800 and contain various pre-treating methods, and the present invention is not limited to these fields.

In Fig. 2, aluminium sheet 1 by bipod roll 32 and niproll 31 transmit to the B direction, the aqueous slkali that gushes out from injection stream 33 etch treatment trough 30 in is handled aluminium sheet 1, and in this installs, can also handle the waste liquid of aqueous slkali simultaneously.By transfer flow container 35, spreading grooves 36, separate out groove 37 and continuous sedimentation thickener 38, drumfilter 39 constitutes treatment system, a part is used as regenerated liquid, a part then is used for Al (OH) ₃Reclaim.

In the etch operation, the concentration of certain NaOH and Al concentration are very important, and it can be regulated by certain proportion and electrical conductivity.The scope of proportion is at central value ± 10%, best ± 7%; On the other hand, the scope of electrical conductivity is at central value ± 20%, best ± 10%.

So-called central value is meant handles suitable NaOH concentration, the proportion of aluminum concentration correspondence and the value of electrical conductivity to etch.Its occurrence cannot treat different things as the same, and is set in as proportion in 1.2～1.6 the scope, preferably is set in 1.3～1.5 the scope; Electrical conductivity generally is set in the scope of 0.15～0.40 (S/cm), is preferably in the scope of 0.2～0.3 (S/cm).

To surpass these adjustable ranges, can produce departing from of aqueous alkali concentration, thereby cause that the asperities degree departs from, the separating out of aluminium, operation go wrong, make the supporter that obtains, and then be lithographic plate quality instability.

In addition, the temperature of aqueous slkali maintains certain value as far as possible.

Handle surface of aluminum plate with aqueous alkali, it is granular residue that its surface can produce undissolved residue, and these residues can be used H ₃PO ₄, HNO ₃, H ₂SO ₄, chromic acid or these materials mixture remove (removing powder residue operation).In the present invention, after etch is handled, when implementing the electrochemistry asperities, require surface of aluminum plate to clean very much, do not have powder residue.But the electrolyte that adopts during the electrochemical treatments of back is acid, when having except that powder residue operation, removes powder residue operation and can omit.

Operation (3): electrochemistry asperities chemical industry preface

For the electrochemistry asperitiesization, the device (as shown in Figure 3) that can use the spy to open to put down in writing in the flat 5-8576 communique.

Among Fig. 3, aluminium sheet 1 transmits to the C direction, carry out electrolytic treatments by first treating apparatus 41 and second treating apparatus 42, first and second treating

apparatus

41,42 and piston rotor 45 and main electrode 44 are installed in the electrolyte 46, and aluminium sheet 1 is processed by piston rotor 45 and main electrode 44.

And this device can be handled the two sides of aluminium sheet, and at the downside of second treating apparatus 42, with the surface upset of aluminium sheet 1, in the asperities treating apparatus 43, piston rotor 45 carries out asperities processing to aluminium sheet 1 back side with main electrode 44 in electrolyte 46 overleaf.Shown in Figure 3, be the device on electrolytic treatments aluminium sheet 1 two sides, and 47 brushes that water for water, aluminium sheet 1 is transported by bipod cylinder 48 and external tapping cylinder 49.

For concrete electrochemistry asperities structure, can be with reference to specifications such as No. 896563, the public clear 48-28123 communiques of spy, BP.And the general sinusoidal ac that always adopts that uses.Open to have write down in the clear 52-58602 communique the spy and can adopt special waveform, open clear 55-158298 number the spy, the spy opens clear 56-28898 number, the spy opens clear 52-58602 number, the spy opens clear 52-152302 number, the spy opens clear 54-85802 number, the spy opens clear 60-190392 number, the spy opens clear 58-120531 number, the spy opens each communique clear 63-176187 number, Te Kaiping 1-5889 number, Te Kaiping 1-280590 number, Te Kaiping 1-118489 number, Te Kaiping 1-148592 number, No. 178496, Te Kaiping, Te Kaiping 1-188315 number, Te Kaiping 1-154797 number, Te Kaiping 2-235794 number, Te Kaiping 3-260100 number, Te Kaiping 3-258600 number, Te Kaiping 4-72079 number, Te Kaiping 4-72098 number, Te Kaiping 3-267400 number, method also can be used described in Te Kaiping 1-141094 number each communique.

Frequency can select to use electrolytic capacitor, in No. 4276129, United States Patent (USP), same No. 4676879 specifications report is arranged all as the aforementioned.

The electrolyte that uses in the electrochemistry asperities chemical industry preface has HNO ₃, HCl etc., foregoing electrolyte also can use, as No. 4671859, United States Patent (USP), with No. 466576, with No. 4661219, with No. 4618405, with No. 462628, with No. 4600482, with No. 4566960, with No. 4566958, with No. 4566959, with No. 4416972, with No. 4374710, with No. 4336113, with mentioned in No. 4184932 specifications.But HNO among the present invention ₃Acid or HCl acid are main.Use HNO ₃Acid or HCl acid when forming uniform convex-concave surface, can be regulated surface configuration according to the difference of electric condition as main component, obtain required performance.

At this, so-called with HNO ₃, HCl is that main component is meant that the main component as electrolyte solution is HNO ₃, HCl.Electrolyte solution of the present invention can be HNO ₃, HCl and other sour mixed liquor, also can contain other micro constitutent.

HNO in the electrolyte solution ₃, HCl concentration, general HCl is 0.5%～5% (weight), best 1%～2%; And HNO ₃Be 0.5%～5% (weight), best 1%～2%; And both are 1%～2% when mixing.

For electrolytic cell, power supply various reports are arranged, adducible have: No. 4203637, United States Patent (USP), spy open clear 56-123400 number, spy and open clear 57-59770 number, spy and open clear 53-12738 number, spy and open clear 53-32821 number, spy and open clear 53-822 number, spy and open clear 53-32823 number, spy and open clear 55-122896 number, spy and open clear 55-132884 number, spy and open clear 62-127500 number, spy and open flat 1-52100 number, spy and open flat 1-52098 number, spy and open clear 60-67700 number, spy and open flat 1-230800 number, spy and open in the flat 3-257199 communique all on the books.

Outside above-mentioned document, many in addition, open clear 52-58602 number as the spy, the spy opens clear 52-152302 number, the spy opens clear 53-12738 number, the spy opens clear 53-12739 number, the spy opens clear 53-32821 number, the spy opens clear 53-32822 number, the spy opens clear 53-32833 number, the spy opens clear 53-32824 number, the spy opens clear 53-32825 number, the spy opens clear 54-85802 number, the spy opens clear 55-122896 number, the spy opens clear 55-132884 number, special public clear 48-28123 number, special public clear 51-7081 number, the spy opens clear 52-133838 number, the spy opens clear 52-133840 number, the spy opens clear 52-133844 number, the spy opens clear 52-133845 number, the spy opens clear 53-149135 number, the spy opens also can using of mentioning in the clear 54-146234 grade.

Electrochemistry asperities chemical industry preface among the present invention in order to grasp the concentration of electrolyte solution, must be regulated electrical conductivity and hyperacoustic velocity of sound of electrolyte.The adjustable range of electrical conductivity is central value deviation ± 20%, be preferably ± 10%.And the adjustable range of hyperacoustic velocity of sound, at central value ± 20%, be preferably ± 10%.

If surpass above-mentioned adjustable range, because of concentration of electrolyte solutions departs from, will cause that the asperities degree departs from, finally cause the plate printing plate supporter that obtains, and then cause the quality instability of lithographic plate.

So-called central value is meant electrical conductivity and hyperacoustic velocity of sound to the suitable concentration correspondence of electrochemistry asperitiesization.Its occurrence cannot treat different things as the same, and the general setting range of electrical conductivity preferably is set in 40～200 (mS/cm) at 10～300 (mS/cm); And hyperacoustic velocity of sound is preferably in 1530～1570 (m/sec) scope generally in 1500～1600 (m/sec) scope.

In addition, the temperature to electric weight and electrolyte solution should be adjusted to certain value as far as possible.

And after the electrochemistry asperitiesization, preferably remove powder residue.

The removal of powder residue requires to carry out with the composition identical with aforesaid electrolyte solution.If use and electrolyte solution heterogeneity solution removal powder residue, need to wash with water again after then removing.So not only cost increases, and has influence on the ash content that electrolysis produces.If with identical composition,, also can be implemented in the temperature of electrochemistry asperities chemical industry preface aspect, the management and the control of concentration even temperature and concentration change.

The method of removing powder residue can also can make solution and plate hight speed impact the removal of pressure powder residue with sprayer etc. with the dissolving method of chemistry.In any case, just passable as long as take all factors into consideration the electrolytic cell shape of productivity ratio, equipment cost, electrochemistry asperitiesization.

That a kind of method no matter wishes to remove 5%～70% powder residue.The amount of the powder residue that produces with electrochemistry asperities chemical industry preface is because of the difference of electrolytic condition has 0.2～5g/m ²Variation, so it is changed in this scope.

After the electrochemistry asperities chemical industry preface (after perhaps removing the powder residue operation), can handle with alkali or acid etch as required, the etch is here handled identical with above-mentioned etch operation.

Etch handle can as the spy open put down in writing in the clear 56-51388 communique with alkali treatment, spy open usefulness sulfuric acid treatment in the clear 53-12739 communique and spy open in the clear 53-115302 communique with the phosphoric acid processing, the spy opens clear 60-8091 number, spy and opens clear 63-176188 number, spy and open flat 1-38291 number, spy and open flat 1-127389 number, spy and open flat 1-188699 number, spy and open flat 3-177600 number, spy and open flat 3-126891 number, spy and the method for mentioning in the communique such as open flat 3-191100 number and also can use.

Aspect above-mentioned etch processing, require to handle as the etch of mentioning in the above-mentioned operation (2).

Operation (4): anode oxide film generates operation

So-called anode oxide film is meant aluminium sheet is carried out electrolysis as anode.Surface at aluminium sheet generates anode oxide film, opens the device (as shown in Figure 4) of flat 8-264118 communique record as using the spy.

In Fig. 4, aluminium sheet 1 transmits to the D direction, and the electric treatment groove 54 of the electrolysis electrode of being furnished with in power supply groove 52 by being furnished with current electrode 56 in the electrolyte 55 and the electrolyte 58 57 makes anode oxidation film-forming.Aluminium sheet 1 is transmitted by cylinder 53.

As main component, such solution can obtain desired hardness as electrolyte to electrolyte of the present invention with sulfuric acid, and simultaneously, required voltage is very low, and this is favourable to industrial production.

Here said with sulfuric acid as main component, the composition that is meant electrolyte is based on sulfuric acid.Electrolyte among the present invention also can adopt the mixed liquor of sulfuric acid and other composition, adds other micro constitutent again.

Other acid of using simultaneously with sulfuric acid has phosphoric acid, chromic acid, bromic acid, sulfamic acid, benzene sulfonic acid etc., or incites somebody to action wherein two or more the combination.

In the electrolyte of the aqueous solution or non-aqueous solution,, then form anode oxide film on the aluminium surface if as anode electric current is passed through aluminium sheet.The treatment conditions of anode oxide film are changed by the variation of electrolyte, and sulfuric acid concentration is in 1%～80% (weight) scope in the general electrolyte, and the liquid temperature is in 5～70 ℃ of scopes, and current density is at 0.5～60A/cm ², voltage 1～100V, electrolysis time is between 15 seconds～50 minutes.

Electrolysis unit leaves clear 48-26638 number, spy the spy and opens in clear 47-18739 number, special public clear 58-24517 number each communique introduction is arranged.And, open clear 54-81133 number, spy the spy and open clear 57-47894 number, spy and open clear 57-51289 number, spy and open clear 57-51290 number, spy and open clear 57-54300 number, spy and open clear 57-136596 number, spy and open clear 58-107498 number, spy and open clear 60-200256 number, spy and open clear 62-136596 number, spy and open clear 63-176494 number, spy and open flat 4-176897 number, spy and open flat 4-280997 number, spy and open flat 6-207299 number, spy and open flat 5-32083 number, spy and open flat 5-125597 number, spy and open the method for putting down in writing in flat 5-195291 number each communique and also can use.

For electrolyte, the spy opens flat 3-253596 number, spy and opens clear 62-82089 number, spy and open flat 1-133794 number, spy and open the electrolyte that clear 54-32424 number, spy open report in flat 5-42783 number and also can use.

Anode oxide film generates in the operation, adjust concentration of electrolyte and aluminum concentration, and this can regulate by electrical conductivity and proportion.The adjustable range that allows electrical conductivity is at central value ± 20%, be preferably in ± 10%; The scope of proportion is at central value ± 10%, be preferably in ± 8%.

If surpass the adjustable range of afore mentioned rules, because concentration of electrolyte departs from, can cause the thickness and the hardness deviation of anode oxide film, the plate printing plate supporter that influence obtains causes lithographic plate quality instability.

Mentioned central value is meant generating anode oxide film suitable concentration of electrolyte and the electrical conductivity of aluminum concentration correspondence and the occurrence of proportion.This value cannot treat different things as the same, and general conductivity setpoint is preferably in 0.30～0.80 (S/cm) scope in 0.10～0.90 (S/cm) scope; Proportion generally is set in 1.05～1.20 scopes, is preferably in 1.08～1.16 scopes.

Behind above-mentioned formation anode oxide film, in order to make plate printing plate supporter and sensitization component that suitable cohesive be arranged, after the anode oxide film etch, utilize steam and hot water to carry out sealing of hole and handle, can obtain the photosensitive printing version that aging stability is good, developing performance is good, not imaging position does not have pollution.The hole sealing device of supporter (special public clear 56-12518 communique) can carry out the post processing that anode oxide film generates operation, and specially opens flat 4-4194 number, spy and open device that flat 5-202496 number, spy open flat 5-179482 number each communique record and can carry out sealing of hole and handle.

Operation (5): hydrophily treatment process

So-called hydrophily treatment process is meant when the hydrophily that the surface is had, water-retaining property improve, for the situation of egative film photosensitive material, also can make itself and the cohesive raising of photosensitive layer.

Handle as hydrophily, handle as the potassium fluorozirconate of reporting in No. 2946638 specifications of United States Patent (USP); The phosphomolybdate of reporting in No. 3201247 specifications of United States Patent (USP) is handled, handling of No. 1108559 records of BP with alkyl titanate, No. 1091433 reports of Deutsche Bundespatent are handled with polyacrylic acid, No. 1134093, Deutsche Bundespatent and No. 1230447 reports of BP are handled with polyvinylphosphonic acid, special public clear 44-6409 communique is put down in writing with the acid treatment of seeing, the record of No. 3307951, United States Patent (USP) is with inositol six acid treatment of seeing, the spy opens clear 58-16893 number and special use organic high molecular compound and the divalent metal salt of opening clear 58-18291 number each communique record handled, record uses the hydrophilic cellulose (as carboxylic formaldehyde cellulose) that contains water-soluble metal salt (inferior plumbous as acetic acid) as priming coat in No. 3860426 specifications of United States Patent (USP), or the special usefulness of opening clear 59-101651 communique record contains the processing of sulfonic water-soluble polymer as bottom, more than these hydrophilies handle and will carry out the adjusting of electrical conductivity and temperature.In addition, what following data was reported is priming coat, and they are: the spy opens the phosphate of clear 62-019494 number record, the spy opens the soluble epoxide compound among the clear 62-033692, the spy opens clear 62-097892 number phosphoric acid acid starch, the spy opens clear 63-056498 number diamine compound, the spy opens clear 63-130391 number amino acid whose inorganic or organic acid, the spy opens organic acid of seeing of carboxyl or the hydroxyl of clear 63-145092, the spy opens the compound of the amino of clear 63-165183 and the acidic group of seeing, the carbonic acid derivative of Te Kaiping 2-316290, the phosphate of Te Kaiping-272594, the compound of Te Kaiping 3-261592 with an amino and a phosphorus oxygen acid root, the phosphate of Te Kaiping 3-215095, aliphatic such as acid or the aromatic series acid of seeing of seeing of the benzene of Te Kaiping 5-246171, the compound of Te Kaiping 1-307745 as sulfur-bearings such as thiosalicylic acids, the compound of the two phosphorus oxygen acid classes of Te Kaiping 4-282637.More than these can be as priming coat, also can dye by the acid dyes that the spy open clear 60-64352 number report.

In the hydrophily treatment process,, must regulate the electrical conductivity and the deviation range thereof of treatment fluid among the present invention for the treatment fluid concentration that is used for the hydrophily processing is regulated, the adjustable range of electrical conductivity, require to be preferably at central value ± 20% ± 10%.

If surpass prescribed limit, the concentration of treatment fluid will depart from, thereby the leather film thickness that produces the hydrophily processing has deviation, finally influences the lithographic plate supporter, makes lithographic plate quality instability.

So-called central value is meant the value of hydrophily being handled the electrical conductivity of suitable concentration of electrolyte correspondence, and its value scope generally is set in 2～60 (mS/cm) scope, and best is in 4～30 (mS/cm) scope.

The state of surface treatment procedure

In the individual operation in above-mentioned among the present invention (1)～(5), to implement three operations at least,, just can guarantee to satisfy certain mass, can be used for making simultaneously the lithographic plate supporter of printing performance excellence if select three operations arbitrarily.

In above-mentioned (1)～(5), wish to carry out following processing:

1. carry out operation (1) or operation (3), operation (2) and (4) three treatment process of operation.

2. carry out in operation (1)～(4), each operation is carried out once or once above processing at least.

3. carry out in operation (2)～(5), each operation is carried out once or once above processing at least.

Carry out in addition above-mentioned (1)～(5) all operations at least once or once above processing, and the whichever operation can repeatedly be carried out.

The processing sequence of these operations is not particularly limited, and operation number (numerical value in the parantheses) can carry out in proper order, also can carry out implementing operation (2) again after operation (3) is handled.

Desirable especially treatment process is exemplified below:

The aluminium sheet of 1. continuous web-like can generate the order enforcement of operation by (1) mechanical asperities chemical industry preface, (2) etch operation, (3) electrochemistry asperities chemical industry preface, (4) anode oxide film, perhaps carries out (5) hydrophilicity-imparting treatment operation again, batches at last.

The aluminium sheet of 2. continuous web-like can perhaps carry out (5) hydrophilicity-imparting treatment operation again by the sequential processes of (2) etch operation, (3) electrochemistry asperities chemical industry preface, (2) etch operation, (4) anode oxide film generation operation, batches at last.

Handle aluminium sheet as above operation listed, make supporter.

[character of surface mass]

1.～4. lithographic plate supporter with method of the present invention is made will satisfy following rerum natura.In the present invention, with material 1.～4. judge whether within the limits prescribed.For the lithographic plate supporter that produces, every 1m ²Area is surveyed 5 points, asks its mean value.Draw difference up and down by the mean value that obtains, judge whether scope in regulation.

Rerum natura 1.

1. rerum natura of the present invention is meant that surperficial arithmetic average roughness (Ra) is in mean value ± 20% scope.

The definition of Ra and assay method have record in JIS B 0601.

If the surperficial arithmetic average roughness Ra of lithographic plate supporter is in above-mentioned scope, just can obtain surfacing, good uniformity, the uniform lithographic plate supporter of printing performance, and then the stable lithographic plate with good quality, printing performance and brush version excellent performance can be provided.

Rerum natura 2.

Rerum natura of the present invention 2. promptly the fineness (L) on surface in the scope of mean value ± 10%, it would be desirable in ± 8%.

The value of relevant (L) is on the books in JIS Z 8729-1980.

As long as (L) in above-mentioned scope, then can obtain even, the bright and clean supporter in surface.And this supporter has good printing performance.

Rerum natura 3.

3. rerum natura of the present invention is characterized by: measure the surface by AFM (measurement range is 100 * 100 (μ m) for AFM, horizontal direction resolution ratio 0.1 μ m), obtain surface area a with approximate line-of-sight course; When the top projected area is b; The value of specific area a/b is in mean value ± 20% scope, and is better at ± 10% o'clock.

The value of aforementioned a/b then can obtain surface area in above-mentioned scope even, do not change the lithographic plate with good evenly brush version performance because of the position with the cementability of photosensitive layer.

Rerum natura 4.

4. rerum natura of the present invention promptly is by AFM (AFM, horizontal direction resolution ratio 1.9 μ m, measurement range is 240 * 240 (μ m)) measure the surface, gradient in ratio that (to contain 30 °) more than 30 ° shared in mean value ± 20% scope, better in ± 10% scope.

Need only the shared ratio of gradient (containing 30 spends) more than 30 degree in above-mentioned scope, it is even just can to obtain concaveconvex shape, and the lithographic plate supporter of good anti-fouling performance is arranged.

B: lithographic plate

As mentioned above, the lithographic plate supporter by the inventive method is made owing to be provided with photosensitive layers such as diazonium compound on its surface, therefore can obtain the lithographic plate of photosensitive property excellence.Below its formation and manufacture method are illustrated.

On the lithographic plate supporter in the present invention, be coated with photosensitive layer at the coating drying nest.At first be coated with the photosensitive layer drying nest and can use applying device (shown in Fig. 5 a, 5b), and drying device (as shown in Figure 6).

Shown in Fig. 5 a, 5b, applying device is that the coated roller 66 of aluminium sheet 1 (lithographic plate supporter) is transmitted to the E direction, simultaneously, deliver to aluminium sheet 1 surface by application roll 66, be coated with the film of last layer coating liquid 65 thus on aluminium sheet 1 surface from the coating liquid 65 that supply opening 68 injects.67 is support unit among Fig. 5 a, the 5b, and 69,69a, 69b be for cutting off parts, 64 for by cutting off the feeding lead-in groove that parts form, and 61 are feeding liquid storage place.

This applying device as long as in constituting application roll 66 is arranged, does not then have other qualification, as: Fig. 5 a and Fig. 5 b shown device can.And the application roll of special public clear 58-4589 communique record also can be used.

As shown in Figure 6, drying system is to constitute like this, and the desiccant hot-air that adds is sent into from the air supply opening 75,77 that is located at a plurality of dry sections, and the air after the processing is got rid of from 76,78 exhaust outlets.Aluminium sheet 1 (lithographic plate supporter) transmits to arrow F direction by 71, is dried by dry section 73,74.In addition, 72 is corresponding with the applying device shown in Fig. 5 a, the 5b.

In the present invention, the photosensitive layer that the surface of lithographic plate supporter forms can be enumerated following embodiment.

[I] contains the situation of the mixed paint of adjacent naphthoquinones azo group sulphonic acid ester and phenol and cresols with the photosensitive layer of phenolic resins

Adjacent benzoquinones azo-based compound, based on following each specification, all on the books on multiple distribution publication, and all these records all have good application, respectively are described as follows: United States Patent (USP) the 2nd, 766, No. 118, same the 2nd, 767, No. 092, the same the 2nd, 772, No. 972, the same the 2nd, 859, No. 112, same the 3rd, 102, No. 809, the same the 3rd, 106, No. 465, the same the 3rd, 635, No. 709, the 3rd, 647, No. 443 together.In these reports, particularly the adjacent naphthoquinones azo group sulphonic acid ester of aromatic carbonyl and adjacent naphthoquinones azo group carboxylate are better.At United States Patent (USP) the 3rd, 635, Jiao's card and the condensation product of acetone and the esterification of adjacent naphthoquinones azo group sulfonic acid of No. 709 specification records, United States Patent (USP) 4,028, containing on the polyester of hydroxyl of No. 111 specification records in molecular end, make adjacent naphthoquinones azo group sulfonic acid or adjacent naphthoquinones azo group carboxylic acid carry out esterification, BP the 1st, 494, the para hydroxybenzene ethylene homo body of No. 043 specification report or and the copolymer of other monomer on allow adjacent benzoquinones azo group sulfonic acid and adjacent benzoquinones azo group carboxylic acid carry out esterification, United States Patent (USP) the 3rd, 750, make on the EVA of p-aminophenyl ethene and other monomer copolymerization adjacent naphthoquinones azo group sulfonic acid and the adjacent naphthoquinones azo group carboxylic acyloxy amination of No. 711 specification records are reacted, and the result is very good.

These o-quinone azo-based compound can be used separately, but wish and alkali soluble resins mixing use.Suitable alkali soluble resins has lacquer resin, and concrete have phenol formaldehyde resin, orthoresol formaldehyde resin, a metacresol formaldehyde resin.In addition, when using the phenolic resins of the 4th, 028, No. 111 reports of United States Patent (USP), if use simultaneously carbon number 3-8 alkyl tert-butyl phenol resin substitution phenolic resins or and the condensation polymer of cresols, formaldehyde, effect will be better.

And, add adjacent benzoquinones azo group-4-sulfonyl chloride, the inorganic anion salt to the azo group diphenylamines, three halogenation methyl oxadiazole compounds, contain three halogenation methyl oxadiazole compounds of benzofurane ring etc. for the formation image that exposes.

As the colouring agent of image, generally use Victoria blue-BOH, gentian violet, oil blue, kiton colors, and special dyestuff of wishing to open with the spy clear 62-29324 communique record.

In addition, have the usefulness of special public clear 57-23253 communique record to contain the sulfuric acid of the alkyl displacement of carbon number 3-15 as sense fat agent, for example with the lacquer resin of tert-butyl phenol, N-octyl phenol, tert-butyl phenol and formaldehyde condensation or make its adjacent benzoquinones azo group-4-that contains this lacquer resin or-5-sulphonic acid ester (opening clear 61-242446 communique as the spy puts down in writing).

And, for better developing performance is arranged, can make it contain the spy and open the said nonionic surface active agent of clear 62-251740 communique.

Above composition can be coated on the supporter to form photosensitive layer with each components dissolved in solvent.Here employed solvent has ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol-methyl ether (methyl cellosolve), glycol-ether (ethyl cellosolve), 2-methoxyacetic acid salt, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl acetate, methyllactic acid, Solactol, methyl-sulfoxide, dimethyl acetamide, N, dinethylformamide, N-methyl pyrrolidone, tetrahydrofurfuryl carbinol, propyl alcohol, diacetone alcohol, methyl alcohol, isopropyl alcohol, diethylene glycol dimethyl ether etc., these solvents may be used alone, can also be used in combination.

The photonasty compositional system that is grouped into by these one-tenth is Gu shape content is at 0.5～3.0g/m ²

[II] contains the photosensitive layer of azo resin, water-fast lipophile optical molecule compound.

As the azo resin, azo resin inorganic salts that are dissolved in organic solvent that the condensation polymer of azo group diphenylamines and formaldehyde or acetaldehyde, chlorophosphate, borofluoride are formed for example, or United States Patent (USP) the 3rd, 300,309 condensation products report, the front and Sulfonates such as tosilate, hypophosphorous acid class such as phenyl hypophosphites, oxyamination compound are as 2, the product of 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid or its salt promptly is dissolved in azo resin acylate of organic solvent or the like.

Among the present invention, the azo resin of other that can utilize has aromatic compound.These aromatic compounds contain an organic group at least, can be carboxyl, sulfonic group, sulfinic acid base, phosphate and hydroxylamino.In addition, the azo resin can also be an azo father-in-law compound, and preferably containing with aromatic series azo father-in-law is the co-condensation polymer of structural units.

Aromatic ring as above preferably contains phenyl and naphthyl simultaneously.

The aforesaid aromatic compound that contains an organic group, can enumerate much as the compound of carboxyl, sulfonic group, sulfinic acid base, phosphate, hydroxylamino, what wish most is 4-methoxyl group benzoic acid, 3-chloro benzoic acid, 2, the 4-dimethoxy-benzoic acid, to phenoxy group benzoic acid, 4-anilino-benzoic acid, phenoxyethanoic acid, phenyl acetic acid, to Para Hydroxy Benzoic Acid, 2,4-dihydroxy benzoic acid, phenylbenzimidazole sulfonic acid, to the acid etc. of seeing of toluenesulfinic acid, 1-naphthalene sulfonic aicd, phosphenylic acid, benzene.Above-mentioned is azo father-in-law salt, particularly diphenylamines-4-azo father-in-law salt that for example special public clear 49-48001 communique of aromatic series azo father-in-law compound of unit is listed with copolycondensation azo resin.

Diphenylamines-4-azo father-in-law salt, obtain by 4-amino-diphenylamines, this class material can have been enumerated: the 4-aminodiphenylamine, 4-amino-3-methoxy diphenylamine, 4-amino-2-methoxy diphenylamine, 4 '-amino-2-methoxy diphenylamine, 4 '-amino-4-methoxy diphenylamine, 4-amino-3 methyl diphenylamine, 4-amino-3-oxethyl diphenylamine, 4-amino-3-beta-hydroxy oxethyl diphenylamine, 4-amino-diphenylamines-2-sulfonic acid, 4-amino-diphenylamines-2-carboxylic acid, 4-amino-diphenylamines-2 '-carboxylic acid etc., good especially is 3-methoxyl group-4-amino-4-diphenylamines, the 4-aminodiphenylamine.

And other azo resin except that aromatic series has: the spy open flat 4-18559 number, the spy opens flat 3-163551 number and the special aldehyde that contains acidic group of opening flat 3-253857 communique report or also can adopt with its azo resin of acetal compound polycondensation.

For azo resin anion and azo resin are formed stable salt and contain organic solvent soluble anion to this resin, these comprise the organic carboxyl acid that contains decane and benzoic acid, contain the organic phosphoric acid and the sulfonic acid of phosphenylic acid etc.Most typical example is that methanesulfonic acid is arranged; TFMS; the fluoro alkanesulfonic acid; lauryl sulfonic acid; the dioctyl sulfosuccinic acid; the dicyclohexyl sulfosuccinic acid; camphorsulfonic acid; toloxyl-3-propane sulfonic acid; Nonylphenoxy-3-propane sulfonic acid; Nonylphenoxy-4-butane sulfonic acid; dibutyl phenoxy group-3-propane sulfonic acid; dinonyl phenoxy group-3-propane sulfonic acid; dibutyl phenoxy group-4-butane sulfonic acid; dinonyl phenoxy group-4-butane sulfonic acid; benzene sulfonic acid; toluenesulfonic acid; Lay sulfonic acid; to chlorobenzenesulfonic acid; 2; the 5-dichloro benzosulfonic acid; sulfosalicylic acid; 2; the 5-acid dimethyl; to acetylbenzene sulfonic acid; 5-nitro-o-toluene sulfonic acid; the 2-nitrobenzene-sulfonic acid; the 3-chlorobenzenesulfonic acid; 3-bromobenzene sulfonic acid; 2-chloro-5-nitrobenzene-sulfonic acid; butyl benzene sulfonic acid; the octyl group benzene sulfonic acid; certain herbaceous plants with big flowers base benzene sulfonic acid; the lauryl benzene sulfonic acid; 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid; isopropyl naphthalene sulfonic acid; the hexyl naphthalene sulfonic acids; dibutyl naphthalene sulfonic acid; the butoxy naphthalene sulfonic acids; the octyl group naphthalene sulfonic acids; the lauryl croceine acid; the dibutyl naphthalene sulfonic acids; the dioctyl naphthalene sulfonic acids; the triisopropyl naphthalene sulfonic acids; the tributyl naphthalene sulfonic acids; 1-naphthol-5-sulfonic acid; naphthalene-1-sulfonic acid; naphthalene-1-sulfonic acid; naphthalene-2-sulfonic acid; 1; 8 dinitronaphthalene-3; the 6-disulfonic acid; the aliphatic and the aromatic sulphonic acid of dimethyl-5-sulfoisophthalate etc.; 2; 2 '; 4; 4 '-tetrahydrotoluene oxygen base benzophenone; 2; 2 '; 4-trihydroxybenzophenone etc. contains-aromatic compound of OH base; and fluorophosphoric acid; fluoboric acid; fluoridize lewis acid; HCLO4; the contour hydracid of HIO4 etc.; be not limited only to these, wherein it is desirable to dibutyl naphthalene sulfonic acid especially; the dibutyl naphthalene sulfonic acids; fluorophosphoric acid; 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid; the lauryl benzene sulfonic acid.Azo resin used in the present invention according to the change of the polycondensation condition when of the molal quantity of each monomer, can obtain the molecular weight of arbitrary value, but in order to realize purpose of the present invention, molecular weight requires about 400～100,000, be preferably 800～8, between 000.

Water insoluble and lipophile macromolecular compound, (1)～(15) class below can enumerating, monomer is as construction unit, and molecular weight is at 1～200,000 EVA usually.

(1) contains acrylic amide, methacryl amine, acrylate, methacrylate, the hydroxy styrenes class of aromatic hydroxyl, as N-(4-hydroxy phenyl) acrylamide and N-(4-hydroxy phenyl) Methacrylamide, neighbour, between, para hydroxybenzene ethene, neighbour,, right-hydroxy phenyl acrylate and methacrylate

(2) contain esters of acrylic acid and the methyl acrylic ester of aliphatic-OH, as 2-hydroxyethylmethacry,ate and 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate

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

(4) alkyl acrylates such as methacrylic acid, ethylacrylic acid, propyl group acrylic acid, butylacrylic acid, amyl group acrylic acid, hexyl acrylic acid, cyclohexyl acrylic acid, octyl group acrylic acid, benzyl acrylic acid, acrylic acid-2-chloroethyl, epihydric alcohol acrylic ester, N-dimethylaminoethyl acrylate

(5) alkylmethacrylates such as methacrylate, ethyl propylene acid esters, propyl methyl acid esters, butyl methyl acrylate, amyl group methacrylate, cyclohexyl methyl acrylate, benzyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate

(6) acrylamide and 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-nitrobenzene acrylamide, N-ethyl-N phenyl acrylamide.

(7) vinyl ethers such as ethyl divinyl ether, 2-chloroethyl vinyl ethers, hydroxyethyl vinyl ethers, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ethers, Vinyl phenyl ether.

(8) vinyl esters such as vinyl acetate, 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) alkenes such as ethene, propylene, isobutene, butadiene, isoprene.

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

(13) the maleic anhydride unsaturated acyl imines such as imines, N-acryloyl group acrylamide, N-propiono Methacrylamide, N-(to the chlorine peroxide benzoyl) Methacrylamide that contract.

(14) methacryl amines such as N-(adjacent aminosulfonyl phenyl) Methacrylamide, N-(an aminosulfonyl phenyl) Methacrylamide, N-(to amino) sulfonyl-phenyl Methacrylamide, N-(1-(3-aminosulfonyl) naphthyl) Methacrylamide, N-(2-aminosulfonyl ethyl) Methacrylamide, and and as above contain identical substituent acrylic amide.Perhaps adjacent aminosulfonyl phenyl methyl acrylate, an aminosulfonyl phenyl methyl acrylate, to methyl acrylic esters such as aminosulfonyl phenyl methyl acrylate, 1-(3-aminosulfonyl phenyl) methacrylates, and the unsaturated sulfamido that contains identical substituent esters of acrylic acid.

(15) contain N-(2-(methacryl hydroxyl)-ester)-2, the contract unsaturated monomer of side chains such as imido, vinyl cinnamate, crosslinked group of 3-dimethyl maleic anhydride, and the monomer copolymerization zoarium that above monomer copolymerization is obtained is also passable.

(16) United States Patent (USP) the 3rd, 751, No. 257 specification reports phenolic resin, for example polyvinyl methylal resin, vinyl-formal resin and polyvinyl acetal resins.

(17) special public clear 54-19773 number, spy open clear 57-904747 number, with 60-182437 number, with 62-58242 number, with 2-123452 number, with 62-123453 number, open the alkali solubility urethanes of flat 2-146042 number record with 63-113450 number, spy.

Above EVA can add polyvinyl butyral resin, polyurethane resin, polyamide, epoxy resin, lacquer phenolic resins, natural resin etc. as required.

The photonasty that is used for supporter of the present invention is formed, for exposed and develops after image, can adopt colouring agent, can enumerate the various colouring agents from colourless to coloured, perhaps this colouring agent is enumerated as follows to the example of different colours variation:

This pigment such as Victoria's ethereal blue-BOH[protects upper valley chemistry society system], oil blue-603#[chemistry society system], patent ethereal blue [Sumitomo three states chemistry society system], gentian violet, bright green, ethyl violet, crystal violet, methyl green, berythromycin, the alkalescence fuchsin, peacock green, oil is purple, between-cresol-purple, rhodamine B, auramine, 4-is right-lignocaine phenyl imidazoles, cyano group-right-lignocaine phenyl acetanil etc. is the triphenylmenthane of representative, diphenyl methane, the oxygen azepine, xanthene, imino group naphthoquinones series, the pigment of azomethine or anthraquinone system.

On the other hand, the colouring agent of variation can be enumerated from colourless to coloured: white color system and with triphenylamine, diphenylamines, adjacent chloro aminobenzen, 1,2,3-triphenyl guanidine, naphthylamines, diaminodiphenyl-methane, right, to the two dimethylamino diphenylamines of ¨ @-, 1,2-diphenylamines ethene, right, to ¨ @, to ¨ @ ¨ @-three dimethylamino triphenylmenthanes, right, to ¨ @-pair-dimethylamino benzhydryl imines, right, to ¨ @, to the adjacent methyl triphenylmenthane of ¨ @ ¨ @-triamido, right, to ¨ @-dimethylamino diphenyl-4-anilino-naphthyl methane, right, to ¨, be the 1st or the 2nd grade arylamine series pigment of representative to ¨ ¨ triaminotriphenyl-methane.Particularly triphenylmenthane etc. is used effectively, and is more preferably triphenylmenthane, diphenyl-methane pigment, especially Victoria's ethereal blue.

Photonasty of the present invention also can be added various additives in forming.

For example, be surfactant (especially the fluorine series of surfactants is effective) for alkyl (as ethyl cellulose, methylcellulose), fluorine series of surfactants, the nonionic that improves the coating performance; For the plasticizer of giving coating flexibility, mar proof (just like polyethylene glycol, ATBC, phthalic acid diethyl, phthalic acid dibutyl, phthalic acid dihexyl, phthalic acid dioctyl, tricresyl phosphate vinyl chloride, tributyl phosphate, trioctyl phosphate, oleic acid oxolane, acrylic acid and methacrylic acid, wherein particularly tricresyl phosphate vinyl chloride is fine); For the sense fat agent of the sense fat that improves image part has (as: spy opens the fatty acid ester of the lacquer of the alcohols of styrene-anhydrous maleic acid EVA of clear 55-527 number record and half ester compound, right-tert-butyl phenol formaldehyde resin with phenolic resins, 50% para hydroxybenzene ethene); Stabilizing agent (for example phosphoric acid, phosphorous acid, citric acid, oxalic acid, chemical pure cholinic acid, benzene sulfonic acid, naphthalene sulfonic acids, sulfosalicylic acid, 4-methoxyl group-2-dihydroxy benaophenonel-5-sulfonic acid, tartaric acid etc.); Developer (as: higher alcohol, anhydrous acid etc.) etc. is used.

Above-mentioned photonasty component is coated on the supporter, need be with photonasty azo resin, lipophile macromolecular compound various additives as required are dissolved in (methyl cellosolve in the appropriate solvent, ethyl cellosolve, dimethoxy-ethane, diethylene glycol methyl ether, diethylene glycol dimethyl ether, 1-methoxyl group-2-propyl alcohol, methyl Cellosolve acetic acid esters, acetone, methyl ethyl ketone, methyl alcohol, N, the N dimethyl formamide, dimethyl acetamide, cyclohexanone, dioxanes, oxolane, methyllactic acid, Solactol, ethylene dichloride, methyl-sulfoxide, water or mixture etc.), be made into coating liquid, then coating, dry getting final product.

Solvent also can use separately, but mixes better for methyl Cellosolve, 1-methoxyl group-2-propyl alcohol, these high boiling solvents of methyllactic acid and methyl alcohol, these low boiling point solvents of methyl ethyl ketone.

Each component concentrations is best in 1%～50% (weight) scope during coating.In this case, the about 0.2～10g/m of its coating amount ²(dry weight) just can, 0.5～3g/m preferably ²

[III] contains the photosensitive layer situation that light two quantizes and photopolymerization is formed.

Quantize to form as light two; can have and on main chain and side chain, contain maleic anhydride contract imines and cinnamyl; cinnamoyl; Chinese cassia tree fork base; Chinese cassia tree fork acetyl group; the polymer of groups such as chalcone base; the maleic anhydride imines that contracts is opened clear 52-988 communique (corresponding United States Patent (USP) 4 at the polymer in the side the spy; 079; No. 041 specification) and Deutsche Bundespatent 2; 626; No. 769 explanations; Deutsches Wirtschafts Patent 21; No. 019; Deutsches Wirtschafts Patent 3; No. 552 specifications reach the polymer of the 163-181 page or leaf record of (DieAngewandte Makromolekulare Chemie) 115 (1983); also have the spy to open clear 49-128991; same 49-128992; same 49-128993; same 50-5376; same 50-5377; same 50-5379; same 50-5378; same 50-5380; same 53-5298; same 53-5299; same 53-5300; same 50-50107; same 51-47940; same 52-13907; same 50-45076; same 52-121700; same 50-10884; with 50-45087 number each communique; Deutsche Bundespatent 2; 349; No. 948; with 2; 616, No. 276 each specification has been reported polymer.

In order to make these polymer be dissolved in aqueous alkali or swelling to be arranged, in polymer, contain carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acids and these sour alkali metal salts and ammonium salt and be the acidic group of 6-12 hydrolysis Pka.As required also can with have above-mentioned acidic group 13 in monomer and contain the contract monomer copolymerizable of imine group of maleic anhydride.The contract acid value of imines polymerization of the maleic anhydride that contains acidic group is preferably in 30～300 scopes, in such polymer, N-[2-(oxidation methyl acryloyl) ethyl by the record of the 71-91 page or leaf of (DieAngewandte Makromolekulare Chemie) 128 (1984)]-2,3-dimethyl maleic anhydride contract imines and methacrylic acid or can use with acrylic acid EVA.And, add the vinyl monomer copolymerization of the 3rd component when synthetic, be easy to be met the multiple EVA of requirement thus.For example: as the vinyl monomer of the 3rd component, acrylate and alkyl acrylate can give EVA with flexibility between the Tg alkyl at high temperature of use homopolymers.

With cinnamyl, cinnamoyl, Chinese cassia tree fork base, Chinese cassia tree fork acetyl group and chalcone base is the photo-crosslinking compound of side chain or main chain, at United States Patent (USP) 3,030, has reported photonasty polyurethane in No. 208 specifications.

The photo-crosslinking compound of buck dissolubility is as follows:

Promptly can enumerating the spy, to open what put down in writing in the clear 60-191244 communique be photosensitive polymer.

Also having the spy to open clear 62-175729, spy opens clear 62-175730, spy and opens that clear 63-25443, spy open clear 63-218944, the spy opens clear 63-218945 number each communique and reported photosensitive polymer.

And, the photosensitive layer that contains these materials can use sensitizer, and sensitizer has: benzophenone inductor, benzanthracene inductor, benzoquinones, aromatic nitro compound, benzothiazole quinoline inductor, thioxanthene ketone, naphthothiazoles inductor, benzothiazole inductor, naphthalene furan ketone compound.Photosensitive layer can use binder and plasticizer as required.Binder is some copolymers, have: haloflex, chlorinated polypropylene, polyalkyl acrylate, acrylonitrile, vinylstyrene, butadiene, etc. wherein a kind of monomer form copolymer or polyamide, methyl cellulose, polyvinyl formal, polyvinyl butyral resin, methacrylic acid copolymer, acrylic copolymer, itaconic acid EVA thing etc.Plasticizer has dibutyl phthalate, dihexyl dibutyl ester, phthalic acid dialkyl, low polyethylene glycol alkoxyl, phosphate etc.Preferably add some and be colored as the dyestuff of purpose or pigment with photosensitive layer and as the materials such as pH value retention agent of agglutinant.

As the composition of photopolymerization photonasty material, unsaturated carboxylic acid and its salt are arranged, the acid amides that ester, unsaturated carboxylic acid and the aliphatic multivalence amines that unsaturated carboxylic acid and aliphatic multivalence alcohol form forms etc.

As Photoepolymerizationinitiater initiater, the alpha-carbonyl compound, acyloin ether, the aromatic series acyloin compound that the α position is replaced by hydrocarbon, quinone compounds, triallyl imidazole dimer/p-aminophenyl ketone, benzothiazole, bifurcation pyridine and compound phenazine, oxadiazole compound etc., these compounds have alkali-soluble or swelling, and have as film-forming high molecular polymer: benzyl () acrylate/() acrylic acid/ethylene monomer copolymer, methacrylic acid/methacrylic acid methyl (methacrylate) copolymer, or with pentaerythrite half ester grafting anhydrous maleic acid anhydride copolymer and acid ethylene copolymer etc.

[IV] electrophotography photosensitive layer

For example, can use United States Patent (USP) 3,001, No. 872 specifications are represented the photosensitive layer of ZnO.Or special open clear 56-161550 number, spy and open clear 60-186847 number, spy and open the electrophotography photosensitive layer of clear 61-238063 communique record.

The consumption of photosensitive layer is the about 0.1～7g/m of dry weighing after coating on the supporter ², be preferably in 0.5～4g/m ²Scope in.

In lithographic plate, for the cohesive that improves supporter and photosensitive layer and the back photosensitive layer that guarantees to develop do not have remaining, or in order to prevent halation, following method commonly used

In order to improve cohesive, the intermediate layer generally is made up of diazo resin and the phosphate cpd, amino-compound, the carbonate compound that are adsorbed on the aluminium.For photosensitive layer after development does not have remainingly, the intermediate layer of being made up of the high material of solubility property is generally with dissolubility good polymer and water-soluble polymer.And in order to prevent halation, dye well UV absorbent is generally contained in the intermediate layer, and intermediate layer thickness can be random, but must be the thickness that photosensitive layer on when exposure and upper strata reacts formation uniformly, and the drying solid of usefulness is 1～100mg/m usually ²The coating ratio, that good especially is 5～40mg/m ²

On the coated photosensitive layer surface layer that is made of separate thrust can also be set, can improve the master film of contact exposure and the vacuum adaptation of sensitive offset press version like this, shorten to arrive the time of vacuum, prevent by bonding bad small destruction when causing exposure.

The method of photosensitive layer coating has the spy to open the fusion-bonding process with the solid powder pulverized of clear 55-12974 communique record, and the spy opens in the clear 58-182636 communique the water in the polymer, uses spray-dired method.That method can, but in the water-based alkaline-based developer that requires this layer to be dissolved in not contain organic solvent, perhaps can remove thus.

The coating that is fabricated onto the photonasty material from the lithographic plate supporter, dry, will form the treating apparatus (series connection) arranged in a straight line of various operations such as aperture plate layer on demand, the aluminium sheet of web-like enters each treatment process as previously mentioned continuously and handles, can make continuously and batch, cheaply lithographic plate.

The material of the roller that in above-mentioned each operation, is used to transmit, shape such as following: can use NBR, UR system rubber, hard chromium plating from the Facing material that passes out to the roller that passes through between the processing.Surface configuration preferably adopts rectilinear form and establishes shape of 13mm * 15mm helicla flute shape, the shape that tapering is arranged, radial projection etc. for preventing to skid.Rolling place roller surface can be used straight shape, is made as the shape of the groove of 15mm.

If by transmitting the connecting plate that operation passes out, then do not need coiled material is connected on the following coiled material, method of attachment at this moment connects with ultrasonic bonding or with electric arc.And can send into operation place adding scraper to adjust web width.

The sensitive offset press version that above method is made, image are exposed the back and form the resin picture of handling with conventional method that image is arranged.For example: the situation of the photosensitive lithographic plate of photosensitive layer is arranged in aforementioned [I], after the portrait exposure, United States Patent (USP) the 4th, 259, No. 434 specifications have write down by aqueous alkali and have developed, and remove exposed portion, obtain lithographic plate; The situation that the photosensitive lithographic plate of photosensitive layer is arranged in [II] after the portrait exposure, at United States Patent (USP) the 4th, 186, has been put down in writing a kind of developer solution in No. 006 specification, the lithographic plate of the development back unexposed portion photosensitive layer that can be removed.And, the spy open clear 59-84241 number, the spy opens clear 57-192952 number and the special lithographic plate video picture of also having reported the positive type in clear 62-24263 number each communique, in fact the water-soluble alkali imaging liquid composition of Shi Yonging opened.

The specific embodiment

Enumerate the comparative example of implementing most preferred embodiment of the present invention and contrasting with it below, so that the present invention is made specific description.But the present invention has more than and is limited to following examples.

＜embodiment 1～4〉(as shown in table 1)

※ tests aluminium sheet

Prepare aluminium sheet, JIS 1050 sheet materials of wide 1030mm, thick 0.24 web-like for experiment usefulness.

The manufacturing of ※ lithographic plate supporter

Below each 1.～6. operation carry out continuously, every example is produced 2000 meters lithographic plate supporter, this moment each operation condition scopes as shown in table 1 below such as treatment fluid concentration.

1. operation (1): mechanical asperities chemical industry preface

Machinery asperities chemical industry preface adopts device shown in Figure 1 to handle.Condition shown in Figure 1 is by following processing, and twice rugosity processing is with same condition.

The transfer rate of aluminium sheet: 30mm/min (following operation speed is identical)

Drum brush diameter: 450mm

The running number of drum brush: 250rpm (direction of transfer of corresponding aluminium sheet)

The kind of abrasive: the quartz sand of average grain diameter 30 μ m evenly distributes

The initial proportion of abrasive: 1.15

In being filled with the jar of abrasive, in order to keep the grinding agent of certain particle diameter, having designed cyclone separator, and, be provided with densimeter in order to measure its proportion.The regulation and control of proportion are as shown in table 1.

2. operation (2): etch operation

1. after the operation,, adopt Fig. 2 device in the above, carry out etch and handle the aluminium sheet washing.The condition of Fig. 2 is as follows:

Treatment fluid kind: the NaOH aqueous solution (initial concentration 25%)

Treatment fluid temperature: 65 ± 0.5 ℃ (certain control)

Treatment fluid initial specific gravity: 1.4

The initial conductivity of treatment fluid: 0.25 (S/cm)

Injection flow: 40L/ root

And, for proportion and the electrical conductivity of measuring treatment fluid, in Agitation Tank, be furnished with densimeter, regulate in proportion and the electrical conductivity scope as shown in table 1.

After etch is handled, with aluminium sheet with the treatment fluid of the electrolyte same composition of the rugosity chemical industry preface of mentioning later in soaked 10 seconds, take off residue treatment.

3. operation (3): electrochemistry asperities chemical industry preface

Through after the above-mentioned 2. operation, device as shown in Figure 3 carries out the asperities processing, at this moment condition following (details is opened in the flat 3-79799 communique the spy and put down in writing, and it is made as 1msec with the growth of ripple).And the condition of the first asperities chemical industry preface, the second asperities chemical industry preface and back side asperities chemical industry preface is identical.

The electrolyte kind: nitric acid (initial concentration 1% (weight)) is main, contains aluminium (concentration 0.4% (weight))

The hyperacoustic initial velocity of sound of electrolyte: 1550m/sec

The initial conductivity of electrolyte: 80mS/cm

Electrolyte temperature: 45 ± 0.5 ℃ (certain control)

Supply frequency: 60HZ

The anode unit quantity of electricity of aluminium sheet: 220c/dm ²

And for ultrasonic velocity and the electrical conductivity of measuring electrolyte, have the various velocities of sound to take into account conductivity meter in electrolyte 46, the velocity of sound and electrical conductivity can be regulated as table 1.

4. operation (2): etch operation

Above-mentioned operation 3. after, with aluminium sheet washing, carry out the etch processing with device shown in Figure 2.The condition of device is as follows:

Electrolyte kind: the NaOH aqueous solution (initial concentration: be main 27%), contain aluminium (concentration 7%)

Treatment fluid temperature: 40 ℃ (certain control)

Treatment fluid initial specific gravity: 1.45

Treatment fluid initial conductivity: 0.27 (S/cm)

Injection flow: 50L/ root

Proportion and electrical conductivity in order to survey treatment fluid are provided with proportion and take into account conductivity meter in groove 35, can be by regulating shown in the table 1.

After the etch, in described later 30% sulfuric acid, soaked 15 seconds, take off residue treatment.

5. operation (4): anode oxide film generates operation

Through operation 4. after, carry out anode oxide film with Fig. 4 device and handle, the condition of device is as follows:

Electrolyte kind: sulfuric acid (initial concentration: be main 15%), also contain aluminium (concentration 1%)

Electrolyte initial specific gravity: 1.15

The initial conductivity of electrolyte: 0.6 (S/cm)

The temperature of electrolyte: 40 ± 0.5 ℃ (certain control)

Supply frequency: 60HZ

The anode unit quantity of electricity of aluminium sheet: 220c/dm2

In order to measure electrolyte density and electrical conductivity.Be provided with densimeter and conductivity meter in the electrolytic treatments groove, its value can be regulated by scope shown in the table 1.

6. operation (5): hydrophilicity-imparting treatment operation

After above-mentioned operation 5.,, carry out hydrophilicity-imparting treatment with the aluminium sheet washing.Specifically, be main treatment fluid (3% the aqueous solution) with sodium metasilicate, temperature remains on 60 ℃, applies by immersion, and the formation adsorbance is 2mg/m ²The hydrophily cortex.

In addition, for proportion and the electrical conductivity of surveying treatment fluid, be provided with proportion in the aforesaid electrolyte treatment trough and take into account conductivity meter, the adjustable range of proportion and electrical conductivity is as shown in table 1.

Table 1:

	①	②		③		④		⑤		⑥
	①	②		③		④		⑤		⑥		Machinery asperities chemical industry preface	The acid etching operation		Electrochemistry asperities chemical industry preface		The etch operation		The anode oxide film production process		The hydrophilicity-imparting treatment operation
	Proportion	Proportion	Electrical conductivity	Hyperacoustic velocity of sound	Electrical conductivity	Proportion	Electrical conductivity	Proportion	Electrical conductivity	Electrical conductivity		Machinery asperities chemical industry preface	The acid etching operation		Electrochemistry asperities chemical industry preface		The etch operation		The anode oxide film production process		The hydrophilicity-imparting treatment operation
	Proportion	Proportion	Electrical conductivity	Hyperacoustic velocity of sound	Electrical conductivity	Proportion	Electrical conductivity	Proportion	Electrical conductivity	Electrical conductivity	Embodiment 1	±5％	±3％	±9％	±10％	±9％	±3％	±7％	±4％	±9％	±9％
Embodiment 2	±7％	±6％	±12％	±14％	±18％	±6％	±15％	±6％	±18％	±15％	Embodiment 1	±5％	±3％	±9％	±10％	±9％	±3％	±7％	±4％	±9％	±9％
Embodiment 2	±7％	±6％	±12％	±14％	±18％	±6％	±15％	±6％	±18％	±15％	Embodiment 3	±9％	±8％	±13％	±18％	±18％	±8％	±18％	±10％	±17％	±17％
Embodiment 4	±10％	±10％	±20％	±20％	±20％	±10％	±20％	±10％	±20％	±20％	Embodiment 3	±9％	±8％	±13％	±18％	±18％	±8％	±18％	±10％	±17％	±17％
Embodiment 4	±10％	±10％	±20％	±20％	±20％	±10％	±20％	±10％	±20％	±20％	Reference example 1	±11％	±3％	±9％	±10％	±9％	±3％	±7％	±4％	±9％	±9％
Reference example 2	±7％	±11％	±12％	±14％	±18％	±6％	±15％	±6％	±18％	±15％	Reference example 1	±11％	±3％	±9％	±10％	±9％	±3％	±7％	±4％	±9％	±9％
Reference example 2	±7％	±11％	±12％	±14％	±18％	±6％	±15％	±6％	±18％	±15％	Reference example 3	±9％	±8％	±21％	±18％	±18％	±8％	±18％	±10％	±17％	±17％
Reference example 4	±8％	±9％	±20％	±21％	±19％	±9％	±17％	±10％	±20％	±20％	Reference example 3	±9％	±8％	±21％	±18％	±18％	±8％	±18％	±10％	±17％	±17％
Reference example 4	±8％	±9％	±20％	±21％	±19％	±9％	±17％	±10％	±20％	±20％	Reference example 5	±11％	±3％	±9％	±10％	±22％	±5％	±7％	±4％	±9％	±9％
Reference example 6	±7％	±11％	±12％	±14％	±18％	±12％	±1 5％	±6％	±18％	±15％	Reference example 5	±11％	±3％	±9％	±10％	±22％	±5％	±7％	±4％	±9％	±9％
Reference example 6	±7％	±11％	±12％	±14％	±18％	±12％	±1 5％	±6％	±18％	±15％	Reference example 7	±9％	±8％	±21％	±18％	±18％	±8％	±23％	±10％	±17％	±17％
Reference example 8	±8％	±9％	±20％	±21％	±19％	±9％	±17％	±12％	±20％	±20％	Reference example 7	±9％	±8％	±21％	±18％	±18％	±8％	±23％	±10％	±17％	±17％
Reference example 8	±8％	±9％	±20％	±21％	±19％	±9％	±17％	±12％	±20％	±20％	Reference example 9	±11％	±3％	±9％	±10％	±22％	±5％	±7％	±4％	±11％	±9％
Reference example 10	±8％	±9％	±20％	±21％	±19％	±9％	±17％	±10％	±20％	±22％	Reference example 9	±11％	±3％	±9％	±10％	±22％	±5％	±7％	±4％	±11％	±9％

The surface physical property evaluation of ※ lithographic plate supporter

For the lithographic plate supporter among each embodiment that is obtained by above method, every 500m measures following rerum natura 1.～4. (per 500 meters be equivalent to per 1 square metre survey 5 points)

Rerum natura is 1.: mean value, maximum and the minimum of a value of surperficial arithmetic average roughness (Ra).

Rerum natura is 2.: the mean value of surface smoothness, minimum and maximum value.

Rerum natura is 3.: (measurement range: 100 * 100 (μ m)) trying to achieve surface area by approximate line-of-sight course is a, and the top projected area is b, the mean value of a/b, maximum and minimum of a value for AFM, horizontal direction resolution ratio 0.1 μ m with AFM.

Rerum natura is 4.: mean value, maximum and the minimum of a value of surveying the ratio of gradient more than 30 degree on surface with AFM.

The manufacturing of ※ lithographic plate

To be cut into 1030 * 800mm by the lithographic plate among each embodiment, each embodiment will prepare.

For all supporters, make its surface form photosensitive layer, method is as follows:

Open the example that flat 11-109637 communique provides according to the spy, its intermediate layer macromolecular compound (table 1) 0.3g, 100g methyl alcohol, 1g water mixes the three, as coating liquid, will apply liquid and be coated in supporting body surface (15mg/m ²), to be dried after, on the top layer that forms will below the sensitization coating liquid said with 1.5g/m ²Amount coating.

The composition of＜photosensitive layer coating liquid 〉

1, the carboxylate of 2-diazo naphthoquinone-5-sulphonyl and benzenetriol-[1,2,3] acetone resin (United States Patent (USP) the 3rd, 635, example 1 is on the books in No. 709 specifications): 0.8g

The linear phenolic resin I:1.5 that following structural formula is arranged

The linear phenolic resin II:0.2g that following structural is arranged

Other resin III:0.4g that following structural formula is arranged

P-n-octyl fluosite (United States Patent (USP) the 4th, 123, on the books in No. 279 specifications): 0.02g

Naphthoquinones-1,2-diazido-4-sulfonic acid chloride: 0.01g

Tetrahydro anhydrous benzene dioctyl phthalate: 0.02g

Benzoic acid: 0.02g

Benzenetriol: 0.05g

4-[p-N, N-two (ethoxy carbonyl alcohol) aminobenzene-2,6-two (trichlorine methyl alcohol)-S-triazine: 0.07g

Victoria ethereal blue-BOH (hodogaya chemical Co., Ltd system anion is replaced acting as a fuel with 1-naphthalene sulfonic aicd): 0.045

F 176 PF (fluorine diagram of system surface-active agent, Japanese ink chemical industrial company system): 0.01g

Butanone: 15g

1-methoxyl group-2-b propanol: 10g

Linear phenolic resin I

Linear phenolic resin II

Other resin III

The evaluation of ※ lithographic plate

Survey its printing characteristic for the lithographic plate that obtains above, specific as follows:

Estimate the means of printing performance

The metal halide lamp of each edition with 3KW exposed 1 minute 1 meter distant place, use following A developer solution or B developer solution.By the made PS processor-900VR of Fuji Photo Film Co Ltd. 30 ℃ of following video pictures 12 seconds.

The composition of＜developer solution A 〉

D-sorbierite: 5.1 parts (weight portion)

The NaOH aqueous solution: 1.1 parts (weight portion)

Triethanolamine, oxirane additive product (30mol): 0.03 part (weight portion)

Water: 93.8 parts (weight portion)

The composition of＜developer solution B 〉

[SiO ₂]/[Na ₂O] mol ratio be 1.2, SiO ₂Account for the sodium silicate aqueous solution of 1.4% (weight): 100 parts

Ethylenediamine hydrate ethylene oxide adduct (30 moles): 0.03 part (weight portion)

With the above lithographic plate that obtains, its life-span and pollutant performance to be estimated, method is as follows:

(a) life-span

The Spring printing machine that utilizes little gloomy printing machine company to make is printed onto till the cisco unity malfunction always, estimates the printability resistance energy according to the number of printing, and printing is many more, and then the life-span is long more.

(b) contaminative

With Heidelberg corporate system SOR-M printing machine, stop after having printed 1000, version is taken out put 30 minutes, 100 on seal on printing machine is again understood contaminative thereafter.

Calculate qualification rate from the result of above printing performance and brush version property, so-called qualification rate is judged with the printing performance that whether can obtain standard.

＜comparative example 1～10〉(as shown in table 1)

In the foregoing description 1～4,, regulate and control each comparative example by the condition and range of table 1 with the various conditions of the treatment fluid of (manufacturing of lithographic plate supporter) each operation.In addition, identical with embodiment 1～4, make 1～10 lithographic plate supporter, measure its physical property, and estimate.

In all embodiments, obtain desirable physical parameter (physical property is 1.～4.), and qualification rate＞98% of printing performance and brush version performance; On the other hand, in comparative example, its physical property index has departs from desirable scope, and the qualification rate of printing performance also drops to 90%.

Adopt the present invention to make the lithographic plate supporter of the method manufacturing of lithographic plate supporter, can make the lithographic plate of certain mass, printing performance and brush version excellent performance.

Claims

1, a kind of manufacture method of lithographic plate supporter is characterized in that: to surface of aluminum plate as supporter, and the processing of at least three operations in operation (1)-(5) below implementing;

Operation (2): with NaOH is Main Ingredients and Appearance, with proportion in central value ± 10% scope, the erosion operation that the aqueous slkali of electrical conductivity in central value ± 20% scope carries out etch to the aluminium sheet table, described proportion central value is 1.2-1.6, and the electrical conductivity central value that described electricity is led is 0.15-0.4S/cm;

Operation (3): with hydrochloric acid or nitric acid is main component, with electrical conductivity in central value ± 20% scope, the electrolyte of ultrasonic velocity in central value ± 20% scope, surface of aluminum plate is carried out the electrochemistry asperities chemical industry preface of electrochemistry asperitiesization, described electrical conductivity central value is 10-300mS/cm, and described ultrasonic velocity central value is 1500-1600m/sec;

Operation (4): with sulfuric acid is main component, with proportion in central value ± 10% scope, the electrolyte of electrical conductivity in central value ± 20% scope, the anode oxide film that surface of aluminum plate is generated oxide-film generates operation, described proportion central value is 1.05-1.20, and described electrical conductivity central value is 0.1-0.9S/cm;

Operation (5) is carried out the hydrophilicity-imparting treatment operation of hydrophilicity-imparting treatment with the electrolyte of electrical conductivity in the scope of central value ± 20% to surface of aluminum plate, and described electrical conductivity central value is 2-60mS/cm.

2, the manufacture method of lithographic plate supporter as claimed in claim 1 is characterized in that: in described operation (1)～(4), each operation is carried out once at least.

3, the manufacture method of lithographic plate supporter as claimed in claim 1 is characterized in that; In described operation (2)-(5), each operation is carried out once at least.

4, the manufacture method of lithographic plate supporter as claimed in claim 1 is characterized in that: in described operation (1)-(5), each operation is carried out once at least.

5, the supporter that obtains of the manufacture method of lithographic plate supporter as claimed in claim 1 is characterized in that: rerum natura was 1.～4. below the physical property of described supporting body surface satisfied:

Rerum natura is 1.: surperficial arithmetic average roughness Ra, in mean value ± 20% scope;

Rerum natura is 2.: surface smoothness, in mean value ± 10% scope;

Rerum natura is 3.: use horizontal direction resolution ratio: 0.1 μ m, and measurement range: the AFM of 100 * 100 μ m is measured the surface, and trying to achieve surface area by approximate line-of-sight course is a, and when the top projected area was b, the value of a/b was in mean value ± 20% scope;

Object is 4.: use horizontal direction resolution ratio: 1.9 μ m, and the AFM of measurement range 240 * 240 μ m is measured the surface, and gradient is 30 ° of ratios more than the degree, in mean value ± 20% scope.