CN1237394C - Producing method for lithographic printing plate originals - Google Patents

Producing method for lithographic printing plate originals Download PDF

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CN1237394C
CN1237394C CN 01104305 CN01104305A CN1237394C CN 1237394 C CN1237394 C CN 1237394C CN 01104305 CN01104305 CN 01104305 CN 01104305 A CN01104305 A CN 01104305A CN 1237394 C CN1237394 C CN 1237394C
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acid
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CN1310359A (en
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上杉彰男
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Fujifilm Corp
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Fujifilm Corp
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Abstract

The invention provides a method for manufacturing an original plate for a lithographic printing plate having improved stability and plate wear resistance of a small halftone dot part or a fine line part, by improving productivity and improving adhesive properties with a photosensitive layer. The method for manufacturing the original plate for the lithographic printing plate comprises the steps of manufacturing an aluminum plate for satisfying requirements of (1) a ratio of an angularity of 30 degrees or more (a30) or 70% or less by measuring in a measuring range of 240 &mu m angle by using an AFM having a resolution of a horizontal (X, Y) direction of 1.9 &mu m, (2) 0.15 &mu m<=Ra<=0.90 &mu m, (3) Rp<=8Ra, and (4) Rmax<=14Ra by roughing/ etching an aluminum substrate by using at least two steps of mechanical roughing, etching and electrochemical roughing, generating an anodized film for controlling an initial current density to a lower site than a terminal current density while maintaining electric conductivity constant to obtain an aluminum support, and forming a photosensitive layer capable of writing with an infrared laser on the support.

Description

The manufacture method of original edition of lithographic printing plate
The invention relates to the manufacture method of original edition of lithographic printing plate, particularly about with aluminium sheet as support, have the manufacture method of the good original edition of lithographic printing plate of the adhesion of good laser explosure adaptability and photographic layer and support.
Be widely used in offset printing with aluminium sheet as the photosensitive lithographic plate of support.The manufacture method of this original edition of lithographic printing plate generally is that the aluminium sheet with lamellar or web-like carries out surface coarsening, carries out anodized again, and painting photosensitive liquid carries out drying, cuts into the size of desired uniformity.With regard to the surface coarsening operation, carrying out the electrochemical surface roughening treatment in acid solution is highly effective for the adhesion that improves with photographic layer.In addition, after anodized, can also carry out surface treatment or coating primary coat liquid, with the adhesion of raising with sensitization liquid.
Particularly in the occasion of the aluminium sheet that uses web-like, can be at painting photosensitive liquid and cut into the size of desired uniformity after carrying out drying, also can coil into web-like and store, cut into the size of needed uniformity then as required.In this manufacture process, the many Zhang Ping's lithographic printing plate masters that cut into given size be stacked bailing.In addition, the original edition of lithographic printing plate that dispatches from the factory after the packing is made a blueprint by the user, and video picture is handled, and also bending process will be carried out in its end in order to be installed on the printing machine, uses just can be installed on the printing machine then.Practicability, that utilize computing machine etc. gradually recently numerical data is used the directly type of directly the retouching original edition of lithographic printing plate of plate-making of infrared laser, is to use laser explosure device to make a blueprint.What this plate-making mode had been known at present has, above-mentioned original edition of lithographic printing plate is installed on the printing cylinder of printing machine, on printing machine, make a blueprint, handle the mode that just can directly print then without video picture, and after making a blueprint on the printing machine or with other exposure device, under the state that is installed on the printing machine, for example utilize the dumping processing solution etc. of printing usefulness to carry out on the machine that video picture handles video picture mode etc.
Directly retouch the photographic layer that uses on the type original edition of lithographic printing plate, different with the photographic layer of in the past the original edition of lithographic printing plate that writes down by ultraviolet exposure by means of the typographical printing film, very thin and light sensitivity are very high mostly, and it is important whether the hardness on support surface and shape homogeneous cause the pass for the good galley of acquisition.Recording method with original edition of lithographic printing plate of such photographic layer can be enumerated: utilize laser to expose, exposure portion is solidified maybe can dissolve, carry out video picture then and handle, depend on to have or not laser radiation, on the surface of original edition of lithographic printing plate, form the method for image portion and non-image portion; Make the recording layer of exposure portion become the method for peelable state; And water wettability and hydrophobicity by exposure change photographic layer surface form the method for image portion and non-image portion etc.With regard to the video picture mode, also the someone has proposed to utilize under the state that is installed on the printing machine dumping processing solution or physical stress to carry out the method for video picture easily.
This structure that has or not laser radiation and form image portion and non-image portion that depends on roughly can be divided into two kinds.A kind of is the method that is called as the photon mode, and this method is to utilize the luminous energy of laser itself to change the method for the rerum natura on photographic layer surface; Another kind is the method that is called as hot mode, this method is to produce heat after absorbing laser, utilizes the heat that is produced to change the rerum natura on photographic layer surface, perhaps utilizes this heat that evaporation and volumetric expansion take place, thereby cause and peel off and disperse etc., remove the method for the part of surface mass.In addition, laser radiation is normally carried out in the very short time, at the position that short time inner laser like this shines, and no matter photon mode or hot mode, the rerum natura on surface all must change.
The employed substrate of the support of original edition of lithographic printing plate in order to improve the adhesion with photographic layer, will carry out the electrolytic surface roughening treatment usually, in addition, keeps the anodic oxidation operation of skin hardness also very important.In the type of directly the retouching original edition of lithographic printing plate that can directly make a plate, in order in the extremely short time, to utilize laser to cause that surface physical property changes, and in order to use aluminium sheet as support, the surface of support must have adhesion and the water-retaining property with the appropriateness of photographic layer, must carry out uniform surface coarsening.So-called surface coarsening uniformly is meant the big or small homogeneous of the pockmark that produces through surface coarsening, and is formed uniformly pockmark on whole surface.These pockmarks for example are difficult for influences such as contaminative and printability resistance for the printing performance of plate very big, and its quality is an important factor in the plate manufacturing.
In recent years, the digital signal of utilizing computing machine etc. the directly system of plate-making comes into vogue gradually along with the development of infosystem, particularly ultrared solid state laser of emission wavelength 760nm-1200nm and semiconductor laser, make high-output power and small-sized device easily, thereby these laser instruments recording light source during as direct plate-making is very useful.For this reason, as the support that original edition of lithographic printing plate is used, wish to develop the halation that can suppress laser, the support that has the key property of galleys such as water-retaining property, water wettability, printability resistance and difficult printing pollution concurrently.
As such can be with the improvement technology of the support of the Image forming material of infrared laser record, for example, disclose among the special public clear 61-48418 and had 5-12g/m at least 2The anodic oxidation support of oxide skin(coating), the spy opens the colloidal sol that disclosing on silver complex compound lining among the clear 63-260491 and having had the nuclear of reduction, has carried out surface coarsening and anodised support.In addition, disclose among the US4555475 silicate processing has been carried out on the surface with anode oxide film, formed 2-8mg/m 2The aluminum support of silicate layer, disclose among the EP164128B sand milling, anodic oxidation carried out in the aluminium surface, silicate is handled then, coated carbon blacks on the gained support is made photosensitive material, forms the method for image.Above-mentioned various technology, though help to improve support water wettability and with the adhesion of recording layer, form on can the pockmark this point of original edition of lithographic printing plate with the desirable homogeneous of support of infrared laser record unsatisfactory.
The present invention considers the problems referred to above and finishes.The objective of the invention is, the manufacture method of the original edition of lithographic printing plate that can stably make is provided, this method can form the pockmark of homogeneous on the whole surface of aluminum support, boost productivity and the adhesion of raising and photographic layer, thereby improve the stability and the printability resistance of little site portion and thin thread part.
The inventor has carried out deep research, and the result is as the character of surface of aluminum support, the pockmark that obtains having the regulation flatness and form the regulation shape, thereby realized above-mentioned purpose, and found to have the creating conditions of aluminum support of this specific character, thereby finished the present invention.Promptly, the present invention is the manufacture method of original edition of lithographic printing plate, it is characterized in that, on aluminium base, adopt the mechanical surface alligatoring, in order to NaOH is that the liquid of main body corrodes and carries out surface coarsening based at least 2 kinds of technologies in the electrochemical surface alligatoring of hydrochloric acid or nitric acid, perhaps surface coarsening and corrosion, the aluminium sheet of following requirement (1)-(4) is satisfied in manufacturing, use then with sulfuric acid, oxalic acid or phosphoric acid are the treating fluid of main body, the different district more than 3 sections of current density is set, and the conductivity of the treating fluid of each section is identical, wherein, the 1st section current density is at 0.1-15A/dm 2Scope, simultaneously the 1st section current density is controlled at than on the low level of the current density of terminal section, the current density of the section between them is the current density between the current density of the 1st section current density and terminal section, electrolyte flow rate is in the 1-250cm/ scope of second, carry out anode oxide film and generate operation, obtain aluminum support, on this support, form the photographic layer that writes with infrared laser.
(1) resolution of usage level direction is that the atomic force microscope of 1.9 μ m is measured in the square scope of 240 μ m, and degree of tilt is proportional more than 30 degree to be in 70%;
(2)0.15μm≤Ra≤0.90μm；
(3)Rp≤8Ra；
(4)Rmax≤14Ra，
Wherein, Ra presentation surface roughness; Rmax represents maximum height; Rp represents the degree of depth of center line.
Wherein, preferably, the aluminum support that obtains through above-mentioned anode oxide film generation operation has the surface texture that satisfies following condition (5).
(5) difference in surface area is more than 10%, below 90%.
So-called difference in surface area, the resolution that is to use horizontal direction is the atomic force microscope of 0.1 μ m, measures surface configuration in the square scope of 50 μ m, establishing the surface area of obtaining with approximate 3 methods is a 1, the top projected area is a 0The time, with % unit representation [(a 1-a 0)/a 0] value of * 100.
Wherein, anode oxide film generates operation preferably to carry out in the following manner, that is, liquid temperature, conductivity and the proportion of the treating fluid of each section all is identical separately.
Be applicable on the original edition of lithographic printing plate of manufacture method of the present invention and be provided with photographic layer, so long as can get final product with the infrared laser record, its structure has no particular limits, can enumerate as representational example: contain infrared absorbent, produce the compound of acid or free radical and by the crosslinked compound of acid or the negative photosensitive layer of free-radical polymerised compound, perhaps contain infrared absorbent, by acidic compound of heat and positive type light sensitive layer etc. with compound of the joint portion of decomposing by acid by heat.
Form in the operation at anode oxide film, change current density stage by stage, control initial stage current density make than latter stage current density low, be not easy to produce current concentration at the anodised initial stage, generate the epithelium of homogeneous, increase current density then, boost productivity, like this, can keep the homogeneity of surfaceness, on whole surface, form the anode oxide film of homogeneous, realize the hydrophiling of support and the adhesion of raising and photographic layer.
Describe the manufacture method of original edition of lithographic printing plate of the present invention below in detail according to starting material and process sequence.
The support that original edition of lithographic printing plate is used, general operating weight is light and the surface is rational, processability and the good aluminium sheet of corrosion resistance.The aluminium that uses for this purpose, can use JIS1050 material, JIS110Q material, JIS1070 material, Al-Mn is that alloy, Al-Mn-Mg are that alloy, Al-Zr are that alloy, Al-Mg-Si are alloy etc.
1. about the JIS1050 material, the technology by inventor's development is disclosed in following patent gazette:
The spy opens clear 59-153861, spy and opens clear 61-51395, spy and open clear 62-146694, spy and open clear 60-215725, spy and open clear 60-215726, spy and open clear 60-215727, spy and open clear 60-216728, spy and open clear 61-272367, spy and open clear 58-11759, spy and open clear 58-42493, spy and open clear 58-221254, spy and open clear 62-148295, spy and open that flat 4-254545, spy open flat 4-165041, special fair 3-68939, the spy opens flat 3-234594, special fair 1-47545 and the spy opens clear 62-140894.
Also has disclosed technology among special fair 1-35910, the special public clear 55-28874 etc. in addition.
2. about the JIS1070 material, the technology by inventor's development is disclosed in following patent gazette:
Te Kaiping 7-81264, spy open flat 7-305133, spy and open that flat 8-49034, spy open flat 8-73974, the spy opens flat 8-108659 and the spy opens flat 8-92679.
3. be alloy about Al-Mg, in following patent gazette, disclose technology by inventor's development:
Special public clear 62-5080, special public clear 63-60823, special fair 3-61753, the spy opens clear 60-203496, the spy opens clear 60-203497, special fair 3-11635, the spy opens clear 61-274993, the spy opens clear 62-23794, the spy opens clear 63-47347, the spy opens clear 63-47348, the spy opens clear 63-47349, the spy opens clear 64-1293, the spy opens clear 63-135294, the spy opens clear 63-87288, special fair 4-73392, special fair 7-100844, the spy opens clear 62-149856, special fair 4-73394, the spy opens clear 62-181191, special fair 5-76530, the spy opens clear 63-30294 and special fair 6-37116.
In addition, also have the spy to open flat 2-215599, spy and open disclosed technology among the clear 61-201747 etc.
4. be alloy about Al-Mn, in following patent gazette, disclose technology by inventor's development:
The spy opens clear 60-230951, the spy opens flat 1-306288 and the flat 2-293189 of Te Kai, also has special public clear 54-42284, special fair 4-19290, special fair 4-19291, special fair 4-19292, spy to open that clear 61-35995, spy open clear 64-51992, the spy opens flat 4-226394, US5009722 and US5028276 etc. in addition.
5. be alloy about Al-Mn-Mg, in following patent gazette, disclose technology by inventor's development:
The spy opens clear 62-86143 and the flat 3-222796 of Te Kai, also has special public clear 63-60824, spy to open that clear 60-63346, spy open clear 60-63347, the spy opens flat 1-293350, EP223737, US4818300, GB1222777 etc. in addition.
6. be alloy about Al-Zr, in following patent gazette, disclose technology by inventor's development:
Special public clear 63-15978 and the clear 61-51395 of Te Kai, the spy opens clear 63-143234 in addition in addition, the spy opens clear 63-143235 etc.
7. be alloy about Al-Mg-Si, disclose relevant technology among the GB1421710.
In order to make the original edition of lithographic printing plate employed aluminum or aluminum alloy plate of support, usually, the aluminum alloy melt liquid to mentioned component and proportioning carries out the cleaning processing at first according to a conventional method, then casting.
During the cleaningization processing, in order to remove the unwanted gases such as hydrogen in the motlten metal, usually handle with degasifier, use the processing that outgas such as argon gas or chlorine, use so-called rigid media filtrator such as ceramic pipe filtrator, ceramic foam filter or filter as the filtrator of filter material or glass cloth filtrator etc., perhaps will outgas and filter to make up and handle with aluminium oxide scale, alumina balls etc.The purpose of carrying out these cleaningization processing is, the defective that prevents the defective that causes owing to foreign matters such as the non-metallic inclusion in the liquation, oxides and prevent to produce by the gas that dissolves in the motlten metal, thereby preferably carry out the cleaning processing.
About the filtration of liquation, open flat 6-57432, spy the spy and open flat 3-162530, spy and open flat 5-140659, spy and open flat 4-231425, spy and open that flat 4-276031, spy open flat 5-311261, the spy opens among flat 6-136466 etc. on the books.
In addition, handle about the degassing of molten metal, the spy open flat 5-51659, real open among the flat 5-49148 etc. on the books.The inventor opens the degassing treatment technology that discloses motlten metal among the flat 7-40017 the spy.
Preceding to address, use through the molten metal of cleaningization processing and cast.The method of casting has, and is the method for using the solid casting mold of representative and the method that drives casting mold with continuous casting process as the use of representative with the DC casting.
When using the DC casting, solidify with 0.5-30 ℃/second cooling velocity.
When being lower than 1 ℃, form many thick intermetallic compounds.
With regard to continuous casting, usually adopting with hunt's method, three C methods in the commercial production is the method for the use chill roll of representative, and is the use salband of representative or the method for cooling block with molten condition rolling method, A Lusiyisi foundry work II type.When adopting continuous casting process, solidify with 100-1000 ℃/second cooling velocity.In general, its cooling velocity is faster than DC casting, thereby can improve the solid solubility of alloying component in aluminum substrate.About continuous casting process, the inventor etc. open flat 3-79798, spy the spy and open flat 5-201166, spy and open flat 5-156414, spy and open flat 6-262203, spy and open that flat 6-122949, spy open flat 6-210406, the spy opens among the flat 6-26308 and is described.
When carrying out the DC casting, can make the ingot casting of thickness of slab 300-800mm.Can adopt conventional method that this ingot casting is carried out face as required and cut, remove 1-30mm, the top layer of 1-10mm preferably.Before and after this, can carry out equal thermal treatment as required.When carrying out equal thermal treatment, become thick in order not make intermetallic compound, should be in the thermal treatment of carrying out under 450-620 ℃ more than 1 hour, below 48 hours.The thermal treatment less than is in the time of 1 hour, all the DeGrain of thermal treatment.
Carry out hot rolling and cold rolling subsequently, make the aluminium milled sheet.Can carry out intermediate annealing before or after hot rolling or in the course of hot rolling handles.The condition of intermediate annealing, be to heat 2-20 hour down at 280-600 ℃ when using periodic annealing furnace, preferably 350-500 ℃ was heated 2-10 hour down, when using continuous annealing furnace, if the programming rate heating with 10-200 ℃/second can make the crystalline structure refinement.
Be finish-machined to the aluminium sheet of thick 0.1-0.5mm by above technology,, can adopt apparatus for correcting such as roll leveller, tension level(l)er to improve its planarity in order to improve planarity.The improvement of face levelling can be carried out after the plate aluminium sheet being cut into one by one, but, in order to boost productivity, preferably to carry out planarity and improve under continuous coiled sheet state.In addition, for plate being processed into the width of regulation, can make it pass through the strip slitting shears production line.In addition, in order to prevent to produce damage, can on surface of aluminum plate, coat very thin oil film owing to aluminium sheet rubs to each other.Described oil film can use the oil film of volatility oil film or involatile as required.About cold rolling, the inventor opens among flat 6-210308 etc. the spy and is described.
In the occasion that casts continuously, for example use the chill roll of hunt's method etc., can directly be continuously cast into the cast sheet of thickness of slab 1-10mm, can save the operation of hot rolling.In addition, use the chill roll of molten condition rolling method etc., can be cast as the cast sheet of thickness of slab 10-50mm, in general, the configuration hot roll is rolled continuously behind casting process, can obtain the continuous casting and rolling plate of thickness of slab 1-10mm.These continuous casting and rolling plates, described identical with the occasion of above-mentioned DC casting, through operations such as supercooling, intermediate annealing, planarity improvement and rip cuttings, be finish-machined to the thickness of slab of 0.1-0.5mm.Intermediate annealing condition and cold rolling condition when using continuous casting process, the inventor opens flat 6-220593, spy the spy and opens flat 6-210308, spy and open flat 7-54111, spy and open among the flat 8-92709 etc. and be described.
In the time of original edition of lithographic printing plate will be used as with the aluminium sheet that said method is made use support,, wish to have following various characteristics according to its purposes.
1. intensity:
In order to obtain the original edition of lithographic printing plate needed deflection of support, 0.2% yield strength should be more than 140MPa.In addition, in order to obtain deflection to a certain degree when carrying out calcination processing, 0.2% yield strength of heating after 3-10 minute should be more than 80MPa, preferably more than 100MPa down at 270 ℃.In the occasion of special requirement deflection, can adopt the aluminum that adds Mg and Mn, on the printing cylinder that fits to printing machine easily, can suitably select the addition of material and micro constitutent according to purposes.About these aspects, the applicant opens flat 7-126820 the spy, the spy opens among the clear 62-140894 and is described.
2. crystalline structure:
The support that original edition of lithographic printing plate is used, when carrying out the processing of chemical surface treatment or electrochemical surface, the crystalline structure owing to surface of aluminum plate causes that surface quality is bad sometimes, the crystalline structure on surface had better not be too thick.The width of crystalline structure is advisable below 200 μ m, preferably below the 100 μ m, preferably below the 50 μ m.The length of crystalline structure is advisable below 5000 μ m, preferably below the 1000 μ m, preferably below the 500 μ m.Open the spy about these the applicant that flat 6-218495, spy open flat 7-39906, the spy opens among the flat 7-124609 and is described.
3. alloying component distributes:
The support that original edition of lithographic printing plate is used, when carrying out the processing of chemical surface treatment or electrochemical surface, the alloying component skewness owing to surface of aluminum plate causes that surface quality is bad sometimes, the alloying component on surface distributes preferably too not inhomogeneous.About this point, the applicant opens the spy that flat 6-48058, spy open flat 5-301478, the spy opens among the flat 7-132689 and is described.
4. intermetallic compound:
The support that original edition of lithographic printing plate is used when carrying out the processing of chemical surface treatment or electrochemical surface, is subjected to the influence of the size and the density of intermetallic compound sometimes.About this point, the applicant opens flat 7-138687 the spy, the spy opens among the flat 4-254545 and is described.
The manner of packing of aluminium sheet for example can be, on carriage made of iron, spread hardboard and felt, corrugated board is put at two ends at product, with plastic flexible pipe integral body is wrapped, inside diameter at coiled sheet inserts wooden ring, peripheral part at coiled sheet is placed felt, tightens with steel band, marks in its external application portion.Wrappage can use polyethylene film, and padded coaming can use Nomex, hardboard.Can adopt other manner of packing in addition, the most important thing is to keep stable, can not produce damage during transportation.
This aluminium sheet carries out surface treatment by the following stated.
At first carry out pre-treatment, the representational example of described pre-treatment can be enumerated, use triclene equal solvent or surfactant to remove the rolling of surface of aluminum plate, and use caustic corrosion agent such as NaOH or potassium hydroxide to handle, clean surface of aluminum plate is come out with oil.
Specifically, the solvent degreasing method has, and uses the method for oil series solvents such as gasoline, kerosene, volatile oil, solvent oil, normal hexane, and uses triclene, methylene chloride, perchloro-ethylene, 1,1, the method for chlorine series solvents such as 1-trichloroethanes.The alkali degreasing method has, use the method for sodium-salt aqueous solutions such as NaOH, sodium carbonate, sodium bicarbonate, sodium sulphate, use the method for the aqueous solution of sodium orthosilicate, sodium silicate, No. two sodium silicate, No. three silicate such as sodium silicate, use the method for aqueous phosphatics such as sodium orthophosphate, sodium orthophosphate dimetallic, tribasic sodium phosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate etc.When using the alkali degreasing method, depend on processing time and treatment temperature, therefore aluminium surface possibility CL must note not taking place the aluminium surface dissolution when ungrease treatment.Adopt the ungrease treatment of surfactant, can use anionic surfactant, cationic surfactant, non-ionic surfactant and amphoteric surfactant.Can use various commercially available prod.Degreasing method can adopt infusion process, spraying process, make the method etc. of wiping then such as infiltration liquid in the cloth etc.In addition, dipping or spraying process also can use ultrasound wave.
Above-mentioned ungrease treatment for example can be opened flat 2-26793 with reference to the spy.
Subsequently, carry out the mechanical surface roughening treatment.The mechanical surface alligatoring has methods such as transfer printing, brushing, liquid blasting, considers that throughput rate also can several method and usefulness.
On aluminium sheet, press the printing transferring method of male and fomale(M﹠F), can make in all sorts of ways.Open clear 60-36195 except above-mentioned spy opens clear 55-74898, spy, the spy opens the clear 60-203496, can also adopt the repeatedly method of transfer printing of the carrying out described in the special flat 4-175945 of hope, and specially is willing to that the surface is flexible method described in the flat 4-204235.
In addition, also can use the roller that carves micro concavo-convex by electrosparking, shot-peening, laser, plasma etching etc. to carry out transfer printing repeatedly, perhaps make and be coated with having of minuteness particle concavo-convex surface and contact with aluminium sheet, exert pressure the repeated multiple times transfer printing ridge design suitable on aluminium sheet in the above repeatedly with the minuteness particle homogeneous diameter.
On transfer roll, form the method for micro concavo-convex, open flat 3-8635, spy the spy and open flat 3-66404, spy and open among the clear 63-65017 etc. and be described.In addition, also can use punching block, lathe tool or laser etc. along 2 directions cut out fine ditch on the roller surface, make on its surface form tetragonal concavo-convex.Known corrosion treatment can be carried out in surface to above-mentioned roller, makes the formed tetragonal concavo-convex fillet that has.Certainly, in order to improve hardness, also can quench, processing such as hard chrome plating.
Below, with reference to the accompanying drawing manufacture method of specification original edition of lithographic printing plate of the present invention one by one.
Fig. 1 is the synoptic diagram of an example of the expression mechanical surface roughening treatment operation of using brush, support by backing roll 107 by the above-mentioned processed plates of making 101 such as aluminium sheet, move along the direction of arrow, uniformly dispersing abrasive pastes 103 on the surface of processed plate 101, make brush roll 102 and on this surface, rotate, carry out the mechanical surface roughening treatment.In this embodiment, dispersed abrasive cream and to handle with the brush roll surface coarsening be to carry out on 2 positions.
In the occasion of using brush, the modulus of elasticity in static bending of bristle is 10000-40000kg/cm 2, 15000-35000kg/cm preferably 2, and deflection is below the 500g, preferably below the 400g, in addition, the particle diameter of used abrasive substance is 20-80 μ m, preferably 30-60 μ m.
The material of brush preferably has above-mentioned physical strength, but also can use the brush beyond the above-mentioned physical strength.For example can from synthetic resin and metal, select.Described synthetic resin for example can be enumerated polyamide such as nylon, polyolefin such as polypropylene, polyester such as Polyvinylchloride, polybutylene terephthalate, polycarbonate etc.Described metal can be enumerated stainless steel, brass etc.
In addition, the material of abrasive material satisfies above-mentioned particle size range and gets final product, and its material is unrestricted, can select from the employed abrasive materials of mechanical surface roughening treatment in the past such as aluminium oxide, silicon dioxide, silit, silicon nitride.
The mechanical surface roughening treatment can be undertaken by following mode, and one side makes the roller brush high speed rotating with above-mentioned bristle, and one side is crimped onto it on surface of aluminum plate, meanwhile brushes to roller and supplies with above-mentioned abrasive material.At this moment, rotating speed, crimp force and the abrasive feeding amount etc. of roller brush have no particular limits.
The employed device of above-mentioned mechanical surface alligatoring for example can be enumerated the spy and open the device described in the clear 50-40047.
Through after the above-mentioned mechanical surface roughening treatment, in order to make aluminium sheet smoothing and homogenising etc., use pH11 is above, preferably the above aqueous slkali of pH13 carries out the chemical corrosion processing to surface of aluminum plate.
Fig. 2 is an example of chemical corrosion treatment process process is carried out in expression to the aluminium surface a synoptic diagram, make aluminium sheet 222 by in the corrosion treatment groove 211 by means of transfer roller 202 and niproll 201, in this treatment trough, utilize liquid-feeding pump 204 (P) will transfer in the liquid bath 205 aqueous slkali via ingress pipe 212, from sprayer 203 at the transversely inject process liquid (based on the corrosive liquid of NaOH) equably of aluminium sheet 222, carry out surface corrosion.When aluminium sheet comes out, utilize the surface of niproll Wiper plate from etching tank, prevent that treating fluid from being taken out of outside the groove.
Modulation treatment liquid in transferring liquid bath 205, the treating fluid that modulates utilizes liquid-feeding pump 204, delivers to sprayer 203 by liquor charging pipe arrangement 212.Come the treating fluid of self-regulated liquid bath, by feeding pipe arrangement 212 ' and 212 from feeding pipe arrangement 212 upper branch ", utilize pump 204 to deliver to spreading grooves 206 respectively or separate out in the groove 207.Can regulate for liquid measure and feeding time by operation setting in pipe arrangement pump (not shown) midway.
Transfer liquid bath and etching tank to couple together by feeding pipe arrangement 212 and recovery liquid pipe arrangement 213, treating fluid circulates between them, in the corrosion treatment process, NaOH composition in the treating fluid reduces along with reaction, aluminium composition increases, moisture is owing to evaporation reduces, and the amount and the constituent concentration for the treatment of fluid change.For this reason, respectively by supply pipe arrangement 220 and 221 supply sodium hydroxide solution and water in the treating fluid of transferring liquid bath, but the aluminium ion that increases can't be removed, and can not aluminium ion be removed by bulking liquor, and it is futile making aluminium ion in the treating fluid remain on the certain density practice by bulking liquor.
For this reason, by feeding pipe arrangement 212 ' and 212 ", a part of transferring the treating fluid in the liquid bath is sent to diffusion dialysis groove 206 in good time and separates out in the groove 207 as the part of the treating fluid that recycles, aluminium ion is discharged to outside the system.In diffusion dialysis groove 206, be recovered as caustic lye of soda by about 70% of the treating fluid of liquor charging, as reclaiming liquid 1., send back in the accent liquid bath by reclaiming with pipe arrangement 218.On the other hand, in the diffusion dialysis groove, form the dialysis waste liquid of oversaturated sodium aluminate solution, be sent to liquid pushing tube 215 by the dialysis waste liquid and separate out in the groove 207 through dialysis.In the diffusion dialysis groove, the water for compensate for evaporation is fallen can add water by feeding pipe arrangement 214.
In separating out groove 207, the dialysis waste liquid of the dialysis of self-diffusion in the future groove mixes with the treating fluid that comes self adjusting grooved, in this mixed liquor, as nucleus, makes crystalline aluminum hydroxide with the aluminium hydroxide seed in the oversaturated sodium aluminate solution.Removed aluminum ions based on the treating fluid of caustic lye of soda and the potpourri of crystalline aluminum hydroxide body, be admitted in the thickener 208 by liquid pushing tube 216, the aluminium hydroxide of crystallization is by pipe arrangement 217, with filter drum 209 syneresis, be collected in the hopper 210, on the other hand, based on the treating fluid of caustic lye of soda, 2. send back in the accent liquid bath by reclaiming with pipe arrangement 219 as reclaiming liquid.Shown in this Fig for using the method for diffusion dialysis, but also can use the crystallization etc. of crystallization.
Etching extent when chemical corrosion is handled is 3g/m 2More than, 25g/m 2Below, 3g/m preferably 2More than, 15g/m 2Below.The not enough 3g/m of etching extent 2The time, the not enough so that concavo-convex smoothing that forms through the mechanical surface roughening treatment can not produce the pockmark of homogeneous when back one section electrolytic treatments.Otherwise etching extent surpasses 25g/m 2The time, above-mentioned concavo-convex disappearance is totally.
Operable aqueous slkali for example can be enumerated: sodium-salt aqueous solutions such as NaOH, sodium carbonate, sodium bicarbonate, sodium sulphate, sodium orthosilicate, sodium silicate, No. two sodium silicate, No. three aqueous silicate solutions such as sodium silicate, aqueous phosphatics such as sodium orthophosphate, sodium orthophosphate dimetallic, tribasic sodium phosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate.
Treatment conditions are, alkaline concentration 0.01%-50% (weight), and 20-90 ℃ of liquid temperature, suitably selected treatment conditions, to reach above-mentioned etching extent at 5 seconds-5 minutes time.
When with above-mentioned aqueous slkali surface of aluminum plate being carried out the chemical corrosion processing, can producing not on its surface, dissolved residue is a dirt.For this reason, can use the described same acid solution of forming of acid solution that uses with the electrolytic surface roughening treatment in back to remove these dirts.
Preferred treatment conditions are 30-80 ℃ of liquid temperature, 3 seconds-3 minutes time.
Subsequently, the aluminium sheet through above-mentioned processing is carried out the electrolytic surface roughening treatment.Electrolytic surface roughening treatment among the present invention preferably utilizes alternation waveform electric current to carry out the 1st and the 2nd electrolytic treatments in acid solution before and after catholyte is handled.Handle by catholyte, generate dirt on the surface of aluminum plate, produce hydrogen simultaneously, can realize the more electrolytic surface alligatoring of homogeneous.
The the 1st and the 2nd electrolytic surface roughening treatment that utilizes exchange current to carry out in acid solution at first is described.It can be identical that the 1st of this electrolytic surface roughening treatment is handled with the 2nd condition of handling, also can be different separately in suitable treatment conditions scope.
Fig. 3 adopts the 1st and the 2nd electrolytic surface roughening treatment aluminum support to be carried out the synoptic diagram of technological process one example of electrolytic surface roughening treatment.
Among Fig. 3, the 301st, aluminum support, on this aluminum support 301,301a is surface (carrying out the face of electrolytic surface roughening treatment at first), 301b is the back side (carrying out the face of electrolytic surface roughening treatment at last).
In addition, the 302nd, be used for the surperficial 301a of aluminum support 301 is carried out the 1st face side roughening treatment device of electrolytic surface alligatoring, 303 also is the 2nd face side roughening treatment device that is used for the surperficial 301a of aluminum support 301 is carried out the electrolytic surface alligatoring, the 304th, and the rear side roughening treatment device that the back side 301b of aluminum support 301 is carried out the electrolytic surface alligatoring.These face side roughening treatment devices 302,303 and rear side roughening treatment device 304, disposed respectively by the AC power (not shown) and be connected to a pair of circular-arc central electrode 306,306 on the electrolytic tank 305, also disposed the cylinder 307 that above central electrode 306, can rotate freely simultaneously.Filling electrolyte 308 between central electrode 306 and cylinder 307.
In addition, between the 1st face side roughening treatment device the 302, the 2nd face side roughening treatment device 303 and rear side roughening treatment device 304, on the position of regulation, a plurality of transfer rollers 309 have been disposed, form the mobile route of aluminum support 201, in addition, mobile route between the 2nd face side alligatoring device 303 and the rear side alligatoring device 304, formed the counter-rotating mobile route 310 that makes aluminum support 301 counter-rotatings, in the feasible side roughening treatment device 304 overleaf, surface 301a contacts with cylinder 307, and back side 301b is impregnated in the electrolytic solution 308.In addition, a plurality of sprayers 311 are set in this counter-rotating mobile route 310, are used for electrolytic solution is spread to aluminum support 301.
When making aluminum support with said apparatus, energising meanwhile makes aluminum support 301 move on the central electrode 306 of each surface coarsening device 302,303,304.Like this, the face side 301a of aluminum support 301 carries out surface coarsening continuously in the 1st face side alligatoring device 302 and the 2nd face side alligatoring device 303.The aluminum support 301 that face side 301a is handled by surface coarsening, by counter-rotating mobile route 310, face side 301a contacts with the cylinder 307 of rear side roughening treatment device 304, and rear side 301b is immersed in the electrolytic solution 308, is sent in the rear side roughening treatment device 304 with such inverted status.When this counter-rotating is mobile in mobile route 310, scatter electrolytic solution by sprayer 311, make aluminum support 301 often be in wetting regime.
This electrolytic surface roughening treatment for example can adopt the electrochemical Gray's method described in special public clear 48-28123, the GB896563 to carry out.Above-mentioned electrolytic method is to use sine-shaped alternating current, but also can use the spy to open the special waveform described in the clear 52-58602.In addition, can also use the spy to open the waveform described in the flat 3-79799.
In addition, can also use the method described in the following patent: the spy opens clear 55-158298, the spy opens clear 56-28898, the spy opens clear 52-58602, the spy opens clear 52-152302, the spy opens clear 54-85802, the spy opens clear 60-190392, the spy opens clear 58-120531, the spy opens clear 63-176187, Te Kaiping 1-5889, Te Kaiping 1-280590, Te Kaiping 1-118489, Te Kaiping 1-148592, Te Kaiping 1-178496, Te Kaiping 1-188315, Te Kaiping 1-154797, Te Kaiping 2-235794, Te Kaiping 3-260100, Te Kaiping 3-253600, Te Kaiping 4-72079, Te Kaiping 4-72098, Te Kaiping 3-267400, Te Kaiping 1-141094.
As frequency, except that above-mentioned, can also use the frequency that in electrolytic condenser, proposes, for example referring to US4276129, US4676879 etc.
Acid solution as electrolytic solution, except nitric acid and hydrochloric acid, can also use the electrolytic solution described in US4671859, US466576, US4661219, US4618405, US462628, US4600482, US4566960, US4566958, US4566959, US4416972, US4374710, US4336113, the US4184932 etc.
The concentration of acid solution is advisable at 0.5-2.5% (weight), considers at above-mentioned dirt and removes use in the processing, and particularly preferred concentration is 0.7-2.0% (weight).In addition, the liquid temperature is 20-80 ℃, particularly preferably is 30-60 ℃.
Proposed various schemes as electrolytic tank and power supply, for example opened clear 56-123400, spy and open clear 57-59770, spy and open clear 53-12738, spy and open clear 53-32821, spy and open clear 53-32822, spy and open clear 53-32823, spy and open clear 55-122896, spy and open clear 55-132844, spy and open clear 62-127500, spy and open flat 1-52100, spy and open flat 1-52098, spy and open that clear 60-67700, spy open flat 1-230800, the spy opens flat 3-257199 referring to US4203637, spy.
Except above-mentioned patent, also proposed various scheme, for example opened clear 52-58602 referring to the spy, the spy opens clear 52-152302, the spy opens clear 53-12738, the spy opens clear 53-12739, the spy opens clear 53-32821, the spy opens clear 53-32822, the spy opens clear 53-32833, the spy opens clear 53-32824, the spy opens clear 53-32825, the spy opens clear 54-85802, the spy opens clear 55-122896, the spy opens clear 55-132884, special public clear 48-28123, special public clear 51-7081, the spy opens clear 52-133838, the spy opens clear 52-133840, the spy opens clear 52-133844, the spy opens clear 52-133845, the spy opens clear 53-149135, the spy opens clear 54-146234.
This electrolytic treatments should be at anode electric weight 30-400C/dm 2, 50-200C/dm preferably 2Condition under carry out.The anode electric weight is lower than 30C/dm 2, can not produce the pockmark of homogeneous; Otherwise, be higher than 400C/dm 2The time, pockmark is excessive.
During the above-mentioned the 1st and the 2nd electrolytic surface roughening treatment, aluminium sheet is subjected to catholyte and handles.Handle through this catholyte, on surface of aluminum plate, generate dirt, produce hydrogen simultaneously, can make the electrolytic surface alligatoring more even.
Catholyte handle be in acid solution, cathode capacity 3-80C/dm 2, 5-30C/dm preferably 2Condition under carry out.Cathode capacity is lower than 3C/dm 2, dirt adhesion amount deficiency; Otherwise, be higher than 80C/dm 2The time, dirt adhesion amount surplus, also inadvisable.
In addition, the solution that electrolytic solution uses in the time of can be with the above-mentioned the 1st and the 2nd electrolytic surface roughening treatment is identical, also can be different.
After the 2nd electrolytic surface roughening treatment, use the above aqueous slkali of pH11 that aluminium sheet is carried out the 2nd chemical corrosion and handle.The aqueous slkali that the pH11 that uses when the 2nd chemical corrosion is handled is above can be identical with the aqueous slkali of use in above-mentioned the 1st chemical corrosion processing, also can use different aqueous slkalis.
But etching extent is different with the 1st chemical corrosion processing, is 0.1-8g/m 2, 0.2-3.0g/m preferably 2, 0.5-1.5g/m preferably 2Etching extent is less than 0.1g/m 2The time, can not make the pockmark edge part that obtains after the electrolytic treatments level and smooth; Otherwise, be higher than 8g/m 2The time, pockmark disappears.
Handle the generation dirt through above-mentioned chemical corrosion, therefore need use, remove above-mentioned dirt with the solution-treated aluminium sheet of sulfuric acid as main body.Described solution based on sulfuric acid except the single solution of sulfuric acid, can also be suitable mixed phosphate, nitric acid, chromic acid, hydrochloric acid etc. and the mixed solution that constitutes.Use with sulfuric acid and remove crude removal, for example can open the method described in the clear 53-12739 and carry out with reference to the spy as the solution of main body.
In addition, also can make up, for example open the method described in the clear 56-51388 and carry out with reference to the spy with alkali treatment.
In addition can also and with the method for putting down in writing in the following patent gazette: the spy opens clear 60-8091, spy and opens clear 63-176188, spy and open flat 1-38291, spy and open flat 1-127389, spy and open flat 1-188699, spy and open that flat 3-177600, spy open flat 3-126891, the spy opens flat 3-191100.
Subsequently, on surface of aluminum plate, form anode oxide film.
Fig. 4 is an example of anodized operation is carried out in expression to surface of aluminum plate a synoptic diagram.
Aluminium sheet 416 moves along the direction of arrow in the figure.In filling with the power supply groove 412 of electrolytic solution 418, make aluminium sheet 416 be with (+) electric charge by transmitting electrode 420.Then, in power supply groove 412, utilize roller 422 that aluminium sheet 416 is carried upward, utilize niproll 424 to make it turn to the below again, carry to electrolytic treatments groove 414 then, utilize roller 428 to convert horizontal direction to.Then, utilize electrolysis electrode 430 to make aluminium sheet 416 be with (-) electric charge, form anode oxide film in its surface, the aluminium sheet 416 that comes out from electrolytic treatments groove 414 is transported to next process.
In above-mentioned anodized device 410, constitute direction throw-over gear by roller 422, niproll 424 and roller 428, between power supply groove 412 and electrolytic treatments groove 414, utilize above-mentioned roller 422,424 and 428 to be chevron and the conveying of falling chevron aluminium sheet 416.Transmitting electrode 420 and electrolysis electrode 430 are connected to direct supply 434-1～434-3.In addition, the nozzle of control flow velocity is 435, the flow velocity in the groove 414 of its control generation oxide film.
In oxide film generated operation, the flow velocity that control generates in the groove (414) of oxide film was crucial for carrying out the interface cooling, generating the homogeneous epithelium, must be controlled at 1-250cm/ second, preferably 5-100cm/ second.In order to control the current density of the groove that generates oxide film, the district more than 3 sections preferably is set, control respectively, the current density of (the 1st section) is controlled on the low level with the initial stage, preferably 0.1-15A/dm 2, 0.5-10A/dm preferably 2In addition, with respect to the current density of final stage, the 1st section current density should be in 60%, preferably in 40%, preferably in 30%.Among Fig. 4,434-1 (initial stage) is the 1st section, and 434-2 is the 2nd section, and 434-3 is the 3rd section (finally).In addition, in Control current density, also will control the concentration of temperature and sulfuric acid etc., these difficult parameters can be controlled by conductivity and proportion with online direct mensuration.
In this occasion, for example in sulfuric acid concentration 50-300g/l, solution below the aluminum concentration 5% (weight), as anodal closure, form anode oxide film with aluminium sheet.Can also allocate phosphoric acid, chromic acid, oxalic acid, sulfaminic acid, benzene sulfonic acid etc. in the above-mentioned solution.
Formed oxide film amount is 1.0-5.0g/m 21.5-4.0g/m preferably 2
Anodised treatment conditions change according to employed electrolytic solution, cannot treat different things as the same, and in general, concentration of electrolyte is 1-80% (weight), 5-70 ℃ of liquid temperature, current density 0.5-60A/cm 2, voltage 1-100V, electrolysis time 15 seconds-50 minutes is adjusted in above-mentioned scope, to reach above-mentioned tunicle amount.
Electrolysis unit leaves clear 48-26638 the spy, the spy opens existing introduction the among clear 47-18739, the special public clear 58-24517.In addition, can use the method for putting down in writing in the following document: the spy opens clear 54-81133, spy and opens clear 57-47894, spy and open clear 57-51289, spy and open clear 57-51290, spy and open clear 57-54300, spy and open clear 57-136596, spy and open clear 58-107498, spy and open clear 60-200256, spy and open clear 62-136596, spy and open clear 63-176494, spy and open flat 4-176897, spy and open flat 4-280997, spy and open flat 6-207299, spy and open flat 5-24377, spy and open that flat 5-32083, spy open flat 5-125597, the spy opens flat 5-195291.
Behind the above formation anode oxide film, for the adhesion that makes each support and photosensitive composition reaches best, behind the corrosion anode oxide film, carrying out sealing of hole with water vapor and hot water handles, can obtain the stability in elapsed time and the photosensitive printing version that good, the non-image position of video picture does not have pollution, the hole sealing device of this support for example has the device described in the special public clear 56-12518, can carry out epithelium with such device and generate aftertreatment.Also can carry out the sealing of hole processing in addition with the apparatus and method that the spy opens among flat 4-4194, the flat 4-33952 of special hope, the special flat 4-33951 of hope, the special flat 3-315245 of hope etc.
In addition, can also carry out following processing: the potassium fluorozirconate described in the US2946638 is handled; Phosphorus order hydrochlorate described in the US3201247 is handled; Alkyl titanate described in the GB1108559 is handled; Polyacrylic acid described in the DE1091433 is handled; Polyphosphoric acid vinyl acetate described in DE1134093 and the GB1230447 is handled; Phosphoric acid described in the special public clear 44-6409 is handled; Phytic acid described in the US3307951 is handled; The spy opens the use lipophilicity organic high molecular compound described in clear 58-16893 and the clear 58-18291 of Te Kai and the salt of divalent metal is handled; By pressing described in the US3860426, setting contains the undercoat of the hydrophilic cellulose (for example carboxymethyl cellulose etc.) of water-soluble metal salt (for example zinc acetate etc.), perhaps open the undercoat described in the clear 59-101651, carry out hydrophilicity-imparting treatment with sulfonic water-soluble polymers by the spy; It is painted perhaps also can to utilize following compounds or dyestuff to carry out: the spy opens the phosphate described in the clear 62-019494, the spy opens the water-soluble oxide of going back described in the clear 62-033692, the spy opens the phosphoric acid modification starch described in the clear 62-097892, the spy opens the diamine compound described in the clear 63-056498, the spy opens the inorganic or organic acids such as amino acid described in the clear 63-130391, the spy opens the organic phospho acid that contains carboxyl or hydroxyl described in the clear 63-145092, the spy opens the compound with amino and phosphonate group described in the clear 63-165183, specific carboxylic acid derivates described in the Te Kaiping 2-316290, phosphate described in the Te Kaiping 3-215095, the compound of the oxyacid base described in the Te Kaiping 3-261592 with 1 amino and 1 phosphorus, phosphate described in the Te Kaiping 3-215095, aliphatics or aromatic series phosphonic acids such as phenyl-phosphonic acid described in the Te Kaiping 5-246171, o-mercaptobenzoic acid described in the Te Kaiping 1-307745 etc. contains the compound of S atom, the undercoat of the compound of the oxyacid group with phosphorus described in the Te Kaiping 4-282637 etc., perhaps the spy opens the acid dyes described in the clear 60-64352.
Be used to atomic force grain microscope (the Atomic Force Microscope that measures among the present invention, hereinafter to be referred as AFM) be the SP13700 that wealthy (セ イ the コ)-electronics industry (strain) of plug is made, measure by the following stated, the aluminium sheet sample that is cut into the square size of 1cm is placed on the horizon sample platform on the piezoelectric scanning instrument, make pole bracket near specimen surface, when arriving interatomic force effect regional, on the XY direction, scan, utilize displacement record sample concavo-convex of the piezoelectricity of Z direction this moment.The scanner that the piezoelectric scanning instrument uses XY150 μ m, Z10 μ m to scan.Pole bracket is the SI-DF20 that NANOPROBE company makes, resonant frequency 120-150KHz, and spring constant 12-20N/m adopts DFM mode (Dynamic Force Mode) to measure.In addition, with the resulting three-dimensional data of least square fitting, reference field is obtained at little inclination angle of compensation sample.
Each character of surface scope of the suitable support that uses in the original edition of lithographic printing plate manufacture method of the present invention is as follows:
(1) difference in surface area is more than 10%, below 90%.So-called difference in surface area, be to use level (X, Y) resolution of direction is the AFM (atomic force microscope) of 0.1 μ m, measures surface configuration in the square scope of 50 μ m, establishing the surface area of obtaining with approximate 3 methods is a 1, the top projected area is a 0The time, with the [(a of % unit representation 1-a 0)/a 0] value of * 100.
(2) usage level (X, Y) resolution of direction is the AFM of 1.9 μ m, measures in the square scope of 240 μ m, the ratio (a30) of degree of tilt more than 30 degree is in 70%.
(3)0.15μm≤Ra≤0.90μm
(4)Rp≤8Ra
(5)Rmax≤14Ra。
In the above-mentioned numerical value, surface roughness Ra is the numerical value of stipulating among the JIS B0601-1994, and the implication of Rp and Rmax is described as follows.
Rmax represents maximum height (Maximun height).
So-called maximum height is meant, by only intercepting datum length on the sectional curve, when clamping the intercepting part, on the vertical multiplying power direction of sectional curve, measure the interval of these 2 straight lines, represent this numerical value with micron (μ m) with 2 straight lines parallel with the average line of this intercepting part.An example of the method for obtaining of maximum height shown in Fig. 5.
Rp represents the degree of depth (Levelling depth) of center line.
Specifically, only intercept datum length from roughness curve, longitudinal separation that will be from the highest summit of this intercepting part to center line is as the degree of depth (with reference to Fig. 6) of center line.
By the definition of center line as can be known, the degree of depth of center line is that the Feng Hegu among Fig. 6 is taken off the numerical value that the interval of the center line that forms at ordinary times and peak by the intercepting part, the straight line parallel with center line is represented with micron (μ m).The degree of depth of this center line is a parameter of the shape of expression roughness curve, and as shown in Figure 6, even Rmax is identical, the value of Rp is also different.When considering contact area big or small relating to contact problems, it is the parameter of a very useful surfaceness.
For the support aluminium sheet that uses among the present invention, shape with above-mentioned characteristic is crucial, when use has above-mentioned scope with the aluminium sheet of external characteristics, for example following point can occur: (1) difference in surface area is less than 10%, poor adhesive force, surpass 90%, the characteristic that is difficult for pollution is often very low; (2) ratio (a30) of degree of tilt more than 30 degree surpasses at 70% o'clock, and it is dirty to be easy to generate ground; When (3) Ra is lower than 0.15 μ m, can not obtain the water-retaining property of appropriateness, be not suitable as printed panel, when Ra surpassed 0.90 μ m, its concavo-convex planarity that might influence photographic layer was difficult for contaminative simultaneously and reduces significantly; When (4) Rp surpassed 8Ra, photographic layer can not thoroughly be removed after the video picture, is easy to generate residual film, and perhaps non-image portion has been easy to generate the pollution of blister; When (5) Rmax surpasses 14Ra, be easy to generate the pollution of blister equally.
On the support that makes with manufacture method of the present invention, photographic layer is set, obtains original edition of lithographic printing plate.The photographic layer of the original edition of lithographic printing plate among the present invention so long as can get final product with the direct-recording photographic layer of infrared laser, has no particular limits, and can enumerate following illustrative photographic layer.
[I] contains the ester of adjacent quinonediazide compound and the photographic layer of alkali soluble resin.
The ester of the compound of adjacent benzoquinones two nitrine can be the adjacent benzoquinones two nitrine sulfonic acid amides or the adjacent benzoquinones two nitrine carboxylic acid amides of adjacent benzene quinone di-azide sulfonic acid ester or adjacent benzoquinones two nitrine carboxylates and aromatic amino compound.
In addition, alkali soluble resin can be enumerated linear phenol-aldehyde resins such as phenol-formaldehyde resin, orthoresol-formaldehyde resin, metacresol-formaldehyde resin; The preferably phenol that replaces with the alkyl of 3-8 carbon atom with the phenolics described in the US4028111 and with tert-butyl benzene resinox etc. or the condensation product of cresols and formaldehyde.
In order to form visual image by exposure, in these compounds, can add adjacent naphthoquinones two triazo-compounds, 4-sulfonic acid chloride, to inorganic anion salt such as diazonium diphenylamine, three halogen methoxyl diazole compounds, have the compounds such as three halogen methoxyl diazole compounds of coumarone ring.Can also add various dyestuffs in addition as colorant.
When forming photographic layer,, be coated on the support then and get final product as long as above-mentioned each composition is dissolved in the solvent.Employed solvent has these solvents such as ethylene dichloride, cyclohexanone, methyl ethyl ketone, glycol monoethyl ether, ethylene glycol monoethyl ether, acetic acid (2-methoxy ethyl) ester, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl-acetic acid ester, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, water, N-Methyl pyrrolidone, tetrahydrofurfuryl carbinol, acetone, diacetone alcohol, methyl alcohol, ethanol, isopropyl alcohol, diethylene glycol dimethyl ether to be used alone, but also also mix together.
To be coated on by the photosensitive composite that these compositions constitute on the support, dividing the calculating coating weight with solid shape is 0.5-3.0g/m 2Photographic layer is set.
About the photographic layer of [I], the inventor formerly spy of submit applications opens in [0027] of flat 11-84675-[0028] section and has a detailed description.
[II] contains the photographic layer of diazo resin and water-insoluble and lipophilicity macromolecular compound.
Diazo resin for example can be enumerated the resultant of reaction azo resin inorganic salts that dissolve in organic solvent to the condensation product of diazonium diphenylamine and formaldehyde or acetaldehyde and hexafluorophosphate, tetrafluoroborate, above-mentioned condensation product and sulfonic acid class (for example p-toluenesulfonic acid or its salt), phosphinic acids salt (for example phenyl-phosphinic acid or its salt), contain the organic solvent solubility diazo resin acylate etc. of resultant of reaction of the compound (for example 2,4 dihydroxyl benzophenone, 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid or its salt) etc. of hydroxyl.
In the present invention, operable other diazo resin be contain have carboxyl, particularly aromatic diazo compound is as the cocondensation compound that constitutes the unit for the aromatics of the oxyacid base of sulfonic group, phosphinic acids base, phosphorus and at least a organic group in the hydroxyl and diazo-compounds, this aromatic ring can be enumerated phenyl, naphthyl etc.
The diazo resin that uses among the present invention, mol ratio and condensation condition by changing each monomer can obtain molecular weight values arbitrarily, and for the purposes of the object of the invention, suitable molecular weight is about 400-100000, preferably about 800-8000.
Water-insoluble and lipophilicity macromolecular compound can be enumerated with the monomer shown in following (1)-(15) and constitute the unit, have a multipolymer of 1-20 ten thousand molecular weight usually as it.
(1) have acrylic amide, methacryl amine, esters of acrylic acid, methyl acrylic ester and the hydroxy styrenes class of aromatic hydroxyl, for example N-(4-hydroxyphenyl) acrylamide or N-(4-hydroxyphenyl) Methacrylamide, neighbour,, para hydroxybenzene ethene, neighbour,, to hydroxyphenyl-acrylate or methacrylate;
(2) have the esters of acrylic acid and the methyl acrylic ester of aliphatic hydroxyl, for example acrylic acid (2-hydroxyethyl) ester or methacrylic acid (2-hydroxyethyl) ester, methacrylic acid (4-hydroxyl butyl) ester;
(3) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, itaconic acid;
(4) (replacement) alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, cyclohexyl acrylate, 2-ethyl hexyl acrylate, benzyl acrylate, acrylic acid-2-chloro-ethyl ester, epihydric alcohol acrylic ester, N-dimethylaminoethyl acrylate;
(5) (replacement) alkyl methyl methyl acrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methyl methacrylate;
(6) acrylamide, Methacrylamide, acrylamide or methacryl amines such as N hydroxymethyl acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-hexyl methyl acrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N phenyl acrylamide, N-nitrobenzophenone acrylamide, N-ethyl-N phenyl acrylamide;
(7) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ether, Vinyl phenyl ether;
(8) vinyl esters such as vinyl acetate, chlorination vinyl acetate, fourth vinegar vinyl acetate, vinyl benzoate;
(9) phenylethylenes such as styrene, α-Jia Jibenyixi, 1-chloro-4-methyl-benzene;
(10) vinyl ketoness such as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone;
(11) olefines such as ethene, propylene, isobutylene, butadiene, isoprene;
(12) N-vinyl pyrrolidone, N-vinylcarbazole, 4-vinylpridine, vinyl cyanide, methacrylonitrile etc.;
(13) the maleic anhydride unsaturated acyl imines such as imines, N-acryloyl group acrylamide, N-vinyl Methacrylamide, N-propiono Methacrylamide, N-(to chlorobenzene formacyl) Methacrylamide that contract;
(14) N-(adjacent amino-sulfonyl phenyl) Methacrylamide, N-(an amino-sulfonyl phenyl) Methacrylamide, N-(to amino) sulfonyl phenyl methyl acrylamide, N-(1-(3-amino-sulfonyl) naphthyl) Methacrylamide, methacryl amines such as N-(2-amino-sulfonyl ethyl) Methacrylamide, and have and above-mentioned same substituent methacryl amine, in addition, adjacent amino-sulfonyl phenyl methyl acrylate, between amino-sulfonyl phenyl methyl acrylate, to amino-sulfonyl phenyl methyl acrylate, methyl acrylic esters such as 1-(3-amino-sulfonyl naphthyl) methacrylate, and have and unsaturated sulfonamide such as above-mentioned same substituent esters of acrylic acid;
(15) N-(2-(methacryloxy)-ethyl)-2,3-dimethyl maleic anhydride contract and have the unsaturated monomer of bridging property base on the side chains such as imines, vinyl cinnamate, also can enable the monomer copolymerizable with above-mentioned monomer copolymerization in addition.
(16) polyvinyl acetal-based resins such as phenolics described in the US3751257 and vinyl-formal resin, polyvinyl butyral resin;
(17) special public clear 54-19773, spy open clear 57-904747, spy open clear 60-182437, spy open clear 62-58242, spy open clear 62-123452, spy open clear 62-123453, spy open clear 63-113450, spy open described in the flat 2-146042, with the liquefiable macromolecular compound of polyurethane alkali.
In above-mentioned multipolymer, also can add polyvinyl butyral resin, urethane resin, polyamide, epoxy resin, linear phenol-aldehyde resin, natural resin etc. as required.
According to application target, in containing the photosensitive composite of these compositions, can and use known adjuvant equally with above-mentioned.The scope of photosensitive composite by solid shape branch concentration 1-50% (weight) is dissolved in the appropriate solvent, is coated on the support, divide the calculating coating weight to be about 0.2-10g/m with solid shape 2, 0.5-3g/m preferably 2Scope, photographic layer is set.
About the photographic layer of [II], the inventor formerly spy of submit applications opens in [0029] of flat 11-84675-[0035] section and has a detailed description.
[III] contains the photographic layer of photodimerization type photosensitive composite and optical polymerism photosensitive composite
Photodimerization type photosensitive composite can be enumerated has the contract polymkeric substance of imido grpup or cinnamyl, cinnamoyl, cinnamylidene, cinnamylidene acetyl group or chalcone base etc. of maleic acid phenates on side chain or main chain.In order to make these polymkeric substance become buck solubility or swelling, in polymkeric substance, contain carboxylic acid sulfonic acid, phosphoric acid, phosphonic acids and their alkali metal salts or ammonium salt and be that the acidic group of 6-12 is useful for the pKa of buck disassociation.In case of necessity, can also make monomer 13 kinds and have the contract monomer copolymerizable of imino group of maleic anhydride with above-mentioned acidic group.
In addition, in containing the photographic layer of these compositions, can use sensitizers such as benzophenone derivates, benzanthrone derivant, quinones, aromatic nitro compound, naphthothiazoles quinoline derivant.
Described optical polymerism photosensitive composite can be enumerated the acid amides etc. of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and salt, unsaturated carboxylic acid and aliphatic polyol compound.
Photoepolymerizationinitiater initiater can use combination, benzothiazole based compound, the trihalomethyl-known initiating agents such as S-triaizine compounds of alpha-carbonyl compound, multinuclear quinone compounds, triallyl imidazole dimer/p-aminophenyl ketone.In addition, as buck solubility or swelling and can film forming high molecular polymer, can enumerate other addition polymerization sex ethylene monomer copolymer, methacrylic acid/methyl methacrylate (or methacrylate) multipolymer of benzyl (methyl) acrylate/(methyl) acrylic acid/use in case of necessity, the product by half ester addition pentaerythrite triacetate on copolymer-maleic anhydride and acid ethylene copolymer etc.
[IV] electrophotography photographic layer
For example can use the ZnO photographic layer described in the US3001872.In addition, can also use the spy to open clear 56-161550, spy and open the photographic layer that clear 60-186847, spy open the use Electrophtography photosensor described in clear 61-238063 etc.
The amount of the photographic layer that is provided with on support is about 0.1-7g/m with the calculating of the dry weight after the coating 2, 0.5-4g/m preferably 2
About the photographic layer of [III] or [IV], the inventor formerly spy of submit applications opens in [0036] of flat 11-84675-[0040] section and has a detailed description.
In these photographic layers, can enumerate as representational example: (1) is contained infrared absorbent, is produced the compound of acid or free radical and by the crosslinked compound of acid or the negative photosensitive layer of free-radical polymerised compound by heat, and (2) contain infrared absorbent, the acidic compound and have positive type light sensitive layer by heat by the compound of sour joint portion of decomposing.
(1) negative photosensitive layer
A kind of as such negative photosensitive layer can enumerate photopolymerization layer.Contain in the photopolymerization layer: (A) infrared absorbent, (B) radical-forming agent (radical polymerization initiator), and (C) cause the free-radical polymerised compound that polyreaction is solidified by the free radical that generates, preferably also contain (D) binder polymer.Infrared absorbent is transformed into heat with the infrared ray that absorbs, and utilizes the heat that is produced to make radical polymerization initiator decomposition such as salt, produces free radical.Free-radical polymerised compound can be from having at least 1 ethene unsaturated double-bond and having at least 1, preferably select the compound of terminal ethene unsaturated link more than 2, utilizes the chain polymerization reaction take place of free radical that generates and solidify.
In addition, as the photographic layer of other form, can enumerate sour cross-linked layer.Contain in the acid cross-linked layer: (E) by light or hot acidic compound (hereinafter to be referred as acid forming agent), (F) the sour crosslinked compound (hereinafter to be referred as crosslinking chemical) that utilize to generate contains in addition be used to form (G) alkali-soluble polymkeric substance layer that contains mentioned component, that can react with crosslinking chemical in the presence of acid.In this acid cross-linked layer, by irradiates light or heating, acid forming agent decomposes, the acid that produced promotes the effect of crosslinking chemical, at crosslinking chemical to each other or form strong cross-linked structure between crosslinking chemical and the binder polymer, and so, alkali-soluble reduces, and is insoluble to developer.At this moment, in order to effectively utilize the energy of infrared laser, in photographic layer, cooperate (A) infrared absorbent.
The following describes each compound that in the recording layer of minus original edition of lithographic printing plate, uses.
[(A) infrared absorbent]
The photographic layer of original edition of lithographic printing plate of the present invention has can be with producing the structure that ultrared laser carries out image recording.In such photographic layer, preferably use infrared absorbent.Infrared absorbent has the effect that the infrared ray that will absorb is transformed into heat.Utilize the heat that generates that radical-forming agent or acid forming agent are decomposed, produce free radical or acid.The infrared absorbent that uses among the present invention is dyestuff or the pigment that has absorption maximum in the 760-1200nm wavelength coverage.
The known dyestuff that described dyestuff can use commercially available dyestuff and for example put down in writing in the document such as " dyestuff brief guide " (Synthetic Organic Chemistry association compiles, clear and published in 45 years).Specifically, for example can enumerate the spy and open the dyestuff of putting down in writing in [0050]-[0051] section of flat 10-39509.
In these dyestuffs, particularly preferredly can enumerate cyanine dye, the female dyestuff of this Valley, storehouse crow, pyralium salt, mercaptan nickel coordination compound, preferentially select cyanine dye for use, particularly by the cyanine dye of following general formula (a) expression.
General formula (a)
In the general formula (a), X 1Expression halogen atom or X 2-L 1Wherein, X 2Expression oxygen atom or sulphur atom, L 1The alkyl of 1-12 carbon atom of expression.R 1And R 2Independent respectively alkyl at 1-12 carbon atom of expression.Consider R from the storage stability of photosensitive layer coating liquid 1And R 2Above alkyl of 2 carbon atoms preferably, preferably, R 1And R 2Be bonded to each other and form 5 Yuans rings or 6 Yuans rings.
Ar 1And Ar 2Can be identical, also can be different, and expression can have substituent aromatic hydrocarbyl.Y 1And Y 2Can be identical, also can be different, expression sulphur atom or 12 dialkyl group methylene that carbon atom is following.R 3And R 4Can be identical, also can be different, and expression can have the following alkyl of substituent 20 carbon atoms.Suitable substituting group can be enumerated 12 carbon atoms following alkoxy, carboxyl, sulfo group.R 5, R 6, R 7And R 8Can be identical, also can be different, expression hydrogen atom or 12 alkyl that carbon atom is following.Consider preferentially to select for use hydrogen atom from the angle of easy acquisition raw material.In addition, Z 1-The expression balance anion.But sulfo group is by R 1-R 8In the occasion that any replaced, Z 1-Be unwanted.Consider preferred Z from the storage stability of photosensitive layer coating liquid 1-Be halogen ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions and sulfonate ion, preferably perchlorate, hexafluorophosphoricacid acid ions and aryl sulfonic acid radical ion.
In the present invention, as the object lesson by the cyanine dye of general formula (a) expression of preferred use, can enumerate the dyestuff that [0017]-[0019] Duan Zhongji of the special flat 11-310623 of hope plants.
The pigment that uses among the present invention can use the pigment of record in commercially available pigment and color index (C. I.) brief guide, " up-to-date pigment brief guide " (Japanese pigment technology association compile, published in 1977), " up-to-date pigment applications technology " (CMC publishes, published in 1986), " the printing-ink technology " (CMC publish, 1984).
The kind of pigment can be enumerated black pigment, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, green pigment, viridine green, fluorescent pigment, metal powder pigment, also has polymer scale to close pigment in addition.The details of these pigment is opened [0052] of flat 10-39509-detailed record of [0054] Duan Zhongyou the spy.They go for the present invention.In these pigment, preferentially select carbon black for use.
In photographic layer, with respect to the general assembly (TW) that the solid shape of photographic layer is divided, the content of above-mentioned dyestuff or pigment is 0.01-50% (weight), preferably 0.1-10% (weight), 0.5-10% (weight) preferably for dyestuff, 1.0-10% (weight) preferably for pigment.
When above-mentioned content was lower than 0.01% (weight), photonasty reduced sometimes, and when surpassing 50% (weight), non-image position produces pollution sometimes when making original edition of lithographic printing plate.
[(B) compound of generation free radical]
The compound of the generation free radical that uses among the present invention can be enumerated shop salt, for example iodine anchor salt, diazonium anchor salt, sulfonium salt.These anchor salt also have the effect that acid generates chaste tree, with free-radical polymerised compound described below and time spent, can play the effect of radical polymerization initiator.Operable wrong salt is the anchor salt by following general formula (b)-(d) expression among the present invention.
General formula (b)
Figure C0110430500271
General formula (c)
Figure C0110430500281
General formula (d)
In general formula (b), Ar 11And Ar 12Expression can have the following aryl of substituent 20 carbon atoms independently respectively.This aryl has substituent occasion, and suitable substituting group can be enumerated halogen atom, nitro, 12 alkyl, 12 alkoxy or 12 aryloxy group that carbon atom is following that carbon atom is following that carbon atom is following.Z 11-Expression is selected from the counterion in halogen ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions and the sulfonate ion, preferably perchlorate, hexafluorophosphoricacid acid ions and aryl sulfonic acid radical ion.
In general formula (c), Ar 21Expression can have the following aryl of substituent 20 carbon atoms.Suitable substituting group can be enumerated halogen atom, nitro, 12 alkyl, 12 alkoxy or 12 aryloxy group, 12 alkyl amino, 12 dialkyl amido, 12 arylamino or 12 ammonia diaryl bases that carbon atom is following that carbon atom is following that carbon atom is following that carbon atom is following that carbon atom is following that carbon atom is following that carbon atom is following.Z 21-Expression and Z 11-The counterion of same implication.
In general formula (d), R 31, R 32And R 33Can be identical, also can be different, and expression can have the following alkyl of 20 substituent carbon atoms.Suitable substituting group can be enumerated halogen atom, nitro, 12 alkyl, 12 alkoxy or 12 aryloxy group that carbon atom is following that carbon atom is following that carbon atom is following.Z 31-Expression and Z 21-The counterion of same implication.
In the present invention, the object lesson of operable salt can be enumerated the salt of putting down in writing in [0030]-[0033] section of the special flat 11-310623 of hope.
The salt that uses among the present invention, preferably very big absorbing wavelength is below 400nm, preferably below the 360nm.Like this, make absorbing wavelength, can under white lamp, carry out the operation of original edition of lithographic printing plate in ultraviolet ray range.
Solid shape with respect to photosensitive layer coating liquid is divided total amount, and these salt are 0.1-50% (weight), 0.5-30% (weight) preferably, and preferably the ratio of 1-20% (weight) is added in the photosensitive layer coating liquid.When addition was lower than 0.1% (weight), photonasty reduced, otherwise when surpassing 50% (weight), non-image produces pollution during printing.These salt can only use a kind, also can more than 2 kinds and use.In addition, these salt can add to other composition with in one deck, also can add to other setting the layer in.
[(C) free-radical polymerised compound]
In the present invention, the free-radical polymerised compound that uses in the photographic layer, be the free-radical polymerised compound that has 1 ethene unsaturated double-bond at least, can be from having 1 at least, preferably having the compound of terminal ethene unsaturated link more than 2 and select.Such compound is being that people know in the art, can use these compounds by without stint in the present invention.The chemical form of these compounds for example can be that monomer, prepolymer are dipolymer, trimer and oligomer, perhaps their potpourri and their multipolymer etc.The example of described monomer and multipolymer thereof can be enumerated unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.), its ester class, amide-type, preferentially selects the amide-type of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and aliphatic polyol compound for use.Can also use the substituent esters of unsaturated carboxylic acids of nucleophilicity such as having hydroxyl, amino, sulfydryl in addition, the addition reaction of amide-type and simple function or polyfunctional isocyanate's class, epoxies is with dehydration condensation thing of simple function or polyfunctional carboxylic acid etc.In addition, can also use the addition reaction of the substituent esters of unsaturated carboxylic acids of electrophilicity such as having isocyanate group or epoxy radicals or amide-type and simple function or polyfunctional alcohols, amide-type and thio-alcohol, and have the esters of unsaturated carboxylic acids of the substituents of leaving away such as halogen or tosyloxy or the substituted reactant of amide-type and simple function and polyfunctional alcohols, amide-type and thio-alcohol.As other example, can also use to replace above-mentioned unsaturated carboxylic acid to be replaced as the compound of unsaturated phosphonic acids, styrene etc.
Object lesson as the acrylate of the free-radical polymerised compound of the ester of aliphatic polyol compound and unsaturated carboxylic acid, methacrylate, itaconate, butenoate, methacrylate, maleate is willing to that the spy Duan Zhongyi is on the books in [0037] of flat 11-310623-[0042], and they can be applicable to the present invention.
As other the example of ester, for example can use special public clear 46-27926, special public clear 51-47334, spy to open the aliphatic alcohol of putting down in writing among the clear 57-196231 is the ester class, the spy opens that clear 59-5240, spy open clear 59-5241, the spy opens the ester of putting down in writing among the flat 2-226149 with aromatic series pastern bone frame, the spy open put down in writing among the flat 1-165613 have an amino ester etc.
In addition, the object lesson of the monomer of the acid amides of aliphatic polyamine compound and unsaturated carboxylic acid has di-2-ethylhexylphosphine oxide-acrylamide, di-2-ethylhexylphosphine oxide-Methacrylamide, 1, the 6-hexa-methylene is two-acrylamide, 1, and the 6-hexa-methylene is two-Methacrylamide, diethylene triamine three acrylamides, xylyl bisacrylamide, the two Methacrylamides of xylyl etc.
Suitable acid amides as other is the example of monomer, and can enumerate the acid amides of putting down in writing among the special public clear 54-21726 with cyclohexene structure is monomer.
In addition, the polyurethane series addition polymerization compound that can also use the addition reaction that utilizes isocyanates and hydroxyl to make, its concrete example for example can enumerate that the vinyl monomer that contains hydroxyl shown in the following general formula of addition (e) obtains on the polyisocyanate compounds that has 2 above isocyanate group in the public clear 48-41708 of spy in per 1 molecule of putting down in writing, contain the vinyl urethane compound of 2 above polymerism vinyl etc. in per 1 molecule.
General formula (e)
CH 2＝C(R 41)COOCH 2CH(R 42)OH
(in the formula, R 41And R 42Expression H or CH 3)
In addition, can also use the spy to open the urethane acrylate class of putting down in writing among clear 51-37193, special fair 2-32293, the special fair 2-16765, the urethane compound class of putting down in writing among special public clear 58-49860, special public clear 56-17654, special public clear 62-39417, the special public clear 62-39418 with oxirane pastern bone frame.
In addition, can also use the spy open clear 63-277653, spy open clear 63-260909, spy open put down in writing among the flat 1-105238, have the free-radical polymerised compound class of amino structure or sulfide based structural in the molecule.
As other example, can enumerate polyfunctional acrylate or methacrylates such as epoxy acrylate class that the spy opens polyester acrylate class, epoxy resin and (methyl) acrylic acid reaction formation put down in writing among clear 48-64183, special public clear 49-43191, the special public clear 52-30490.In addition, can also enumerate the unsaturated compound of putting down in writing among special public clear 46-43946, special fair 1-40337, the special fair 1-40336, the spy opens the vinyl phosphonate based compound put down in writing among the flat 2-25493 etc.The structure that contains perfluoroalkyl that can also use the spy to open to put down in writing among the clear 61-22048 in some occasion.In addition, can also use in Japan and follow in the will vol.20 of association, № 7, the 300-308 page or leaf (1984) compound of introducing as photo-curable monomer and oligomer.
About these free-radical polymerised compounds, use what kind of structure, the independent use still and usefulness, addition is how, and the concrete condition of these using method can be selected suitable structure, cooperation and addition arbitrarily according to the performance design of final record material.In addition, can also adopt primary coat according to occasion, go up coating structure and coating process.
[(D) binder polymer]
Also use binder polymer in the present invention.Described bonding agent preferably uses the line style organic polymer.Like this " line style organic polymer " can use any.In order to carry out water video picture or the video picture of weak base water, preferably select the line style organic polymer of water or weak base water dissolvable or swelling.Described line style organic polymer can be according to forming agent as the epithelium that is used to form photographic layer and selecting to use as the purposes of water, weak base water or organic solvent developer.For example, when using water-soluble organic polymer, can carry out the water video picture.Such line style organic polymer has, the free radical polyalcohol that has carboxyl on the side chain, for example specially open clear 59-44615, special public clear 54-34327, special public clear 58-12577, special public clear 54-25957, spy and open that clear 54-92723, spy open clear 59-53836, the spy opens the free radical polyalcohol of putting down in writing among the clear 59-71048, be i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, butenoic acid multipolymer, maleic acid, partial esterification maleic acid etc.The acid cellulose derivant that on side chain, has the carboxylic acid group in addition in addition.In addition, can also use at addition product with addition cyclic acid anhydride on the polymkeric substance of hydroxyl.
Wherein, (methyl) acryl resin that has benzyl or allyl and carboxyl on the side chain has the balance of good film strength, photonasty and video picture, thereby is preferentially selected for use.
In addition, special fair 7-12004, special fair 7-120041, special fair 7-120042, special fair 8-12424, spy open clear 63-287944, spy, and to open the urethanes that contain acidic group that clear 63-287947, spy open record among flat 1-271741, the special flat 10-116232 of hope etc. be adhesive resin, intensity is very good, considers it is very favourable from printability resistance and the adaptive angle of low exposure.
In addition, can use polyvinylpyrrolidone and polyoxyethylene etc. as the water soluble linear organic polymer.In addition,, can also use pure soluble nylon or 2, the polyethers of 2-pair-(4-hydroxyethyl)-propane and chloropropylene oxide in order to improve the intensity of cured film.
The polymkeric substance that uses among the present invention, its weight-average molecular weight be preferably more than 5000, and preferably 10,000-300,000, preferably more than 1000, preferably 2000-25 ten thousand for number-average molecular weight.Polydispersity (weight-average molecular weight/number-average molecular weight) is being advisable more than 1, preferably the scope of 1.1-10.
These polymkeric substance can be that atactic polymers, block polymer, graft polymer etc. are any, preferably atactic polymers.
The polymkeric substance that uses among the present invention can adopt in the past known method synthetic.The solvent that uses when synthetic for example can be enumerated tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, glycol monomethyl ether, ethylene glycol monoethyl ether, acetate (2-methoxy ethyl) ester, diethylene glycol dimethyl ether, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl-acetic acid ester, N, dinethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water etc.These solvents can be used singly or two or more kinds mixed.
The free radical polyalcohol polymerization initiator that uses during the polymkeric substance used in synthetic the present invention can use known compounds such as azo series initiators, peroxide initiator.
The binder polymer that uses among the present invention can be used alone, but also also mix together.Solid shape with respect to photosensitive layer coating liquid is divided total amount, and the adding proportion of these polymkeric substance in photographic layer is 20-95% (weight), preferably 30-90% (weight).The occasion of addition less than 20% (weight), the undercapacity of image portion when forming image; Otherwise, when addition surpasses 95% (weight), can not form image.In addition, the compound with ethene unsaturated double-bond that can free radical polymerization and the weight ratio of linear organic polymer are advisable in the scope of 1/9-7/3.
The following describes the constituent of sour cross-linked layer.The infrared absorbent that uses in this layer can use with above about the same material of photopolymerization layer described (A) infrared absorbent.
Solid shape with respect to photographic layer is divided total amount, and its content is advisable at 0.01-50% (weight), 0.1-10% (weight) preferably, 0.5-10% (weight) preferably for dyestuff, 1.0-10% (weight) preferably for pigment.
When above-mentioned content was lower than 0.01% (weight), photonasty can reduce sometimes, and when being higher than 50% (weight), non-image portion pollutes sometimes when making original edition of lithographic printing plate.
[(E) acid forming agent]
In the present embodiment, decomposing acidic acid forming agent by heat is meant the light by irradiation 200-500nm wavelength or is heated to more than 100 ℃ and acidic compound.
Described acid forming agent can acidic known compound and their potpourri after can enumerating the thermal decompositions of using in light depigmenting agent, phototropic agent or the microsistor etc. of light trigger, pigment of light trigger, the optical free radical polymerization of light cationic polymerization such as known acid forming agent.
For example: S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal et al, Polymer, the diazo salts of record in 21,423 (1980); US4069055, spy open the middle ammonium salts of putting down in writing such as flat 4-365049; Record De phosphonium salt among US4069055, the US4069056; EP104143, US339049, US410201, spy open flat 2-150848, the spy opens the salt compounded of iodine of putting down in writing among the flat 2-296514; The sulfonium salt of putting down in writing among EP370693, EP390214, EP233567, EP297443, EP297442, US4933377, US161811, US410201, US339049, US4760013, US4734444, US2833827, DE2904626, DE3604580, the DE3604581; J.V.Crivello et al, Macromolecules, 10 (6), 1307 (1977), J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., the salt of record in 17,1047 (1979); C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, record clock salt among the p478 Tokyo, Oct (1988); US3905815, special public clear 46-4605, spy open clear 48-36281, spy and open clear 55-32070, spy and open clear 60-239736, spy and open clear 61-169835, spy and open clear 61-169837, spy and open clear 62-58241, spy and open that clear 62-212401, spy open clear 63-70243, the spy opens the organohalogen compounds of putting down in writing among the clear 63-298339; Organic metal/organohalogen compounds of putting down in writing among the Te Kaiping 2-161445; EP0290750, EP046083, EP156535, EP271851, EP0388343, US3901710, US4181531, spy open clear 60-198538, the spy opens the optical acid generating agent of putting down in writing among the clear 53-133022 with adjacent nitrobenzyl fundamental mode protecting group; EP0199672, EP84515, EP199672, EP044115, EP0101122, US4618564, US4371605, US4431774, spy open clear 64-18143, spy, and to open what put down in writing among flat 2-245756, the special flat 3-140109 of hope be the compound that the photolysis of representative produces sulfonic acid with imino group sulfonate; The spy opens two sulphones of putting down in writing among the clear 61-166544.
In addition, can also enumerate and import the compound that produces these sour groups or compound and obtain on the main chain of polymkeric substance or side chain, for example US3849137, DE3914407, spy open clear 63-26653, spy and open clear 55-164824, spy and open clear 62-69263, spy and open clear 63-146037, spy and open that clear 63-163452, spy open clear 62-153853, the spy opens the compound of putting down in writing among the clear 63-146029.
In addition, can also use V.N.R.Pillai, Synthesis, (1), 1 (1980), A.Abad et al, Tetrahedron Lett., (47) 4555 (1971), D.H.R.Barton et al, J.Chem.Soc., (B), 329 (1970), the acidic compound put down in writing among US3779778, the EP126712 by means of light.
In above-mentioned acid forming agent, preferentially select compound for use by following general formula (I)-(V) expression.
Figure C0110430500343
Ar 1-SO 2-SO 2-Ar 2 (IV)
In above-mentioned (I)-(V), R 1, R 2, R 4And R 5Can be identical, also can be different, and expression can have the following alkyl of substituent 20 carbon atoms.R 3Represent halogen atom, can have the following alkyl of substituent 10 carbon atoms or 10 alkoxys that carbon atom is following.Ar 1And Ar 2Can be identical, also can be different, and expression can have the following aryl of substituent 20 carbon atoms.R 6Expression can have the alkyl of substituent 20 following divalents of carbon atom.N represents the integer of 0-4.
In the above-mentioned general formula, R 1, R 2, R 4And R 5The alkyl of 1-14 carbon atom preferably.
By the optimal way of the represented acid forming agent of above-mentioned general formula (I)-(V), the inventor formerly spy of submit applications is willing to existing detailed explanation in the section of [0197] of flat 11-320997-[0222].These compounds for example can adopt the spy to open flat 2-100054, the spy opens the method described in the flat 2-100055 and synthesizes.
In addition, as above-mentioned (E) acid forming agent, can also enumerate with the salt as counterion such as halogenide or sulfonic acid, wherein, preferentially select the compound that has by any structural formula in the salt compounded of iodine of following general formula (VI)-(VIII) expression, sulfonium salt, the diazo salt for use.
Ar 3-I +-Ar 4X -General formula (VI)
Figure C0110430500351
General formula (VII)
Ar 3-N 2 +X -General formula (VIII)
In above-mentioned general formula (VI)-(VIII), X -Expression halide ion, ClO 4 -, PF 6 -, SbF 6 -, BF 4 -Or R 7SO 3 -, wherein, R 7Expression can have the following alkyl of substituent 20 carbon atoms.Ar 3And Ar 4Expression can have the following aryl of substituent 20 carbon atoms independently respectively.R 8, R 9And R 10Expression can have the following alkyl of substituent 18 carbon atoms.
Such salt, the compound of opening the general formula (I)-(III) in the section of [0010] of flat 10-39509-[0035] the spy is on the books.
Solid shape with respect to recording layer is divided total amount, and the addition of acid forming agent is advisable at 0.01-50% (weight), preferably 0.1-25% (weight), preferably 0.5-20% (weight).
If above-mentioned addition is less than 0.01% (weight), can not obtain image sometimes, if surpass 50% (weight), when making original edition of lithographic printing plate, non-image sometimes can be polluted in the process of printing.
Above-mentioned acid forming agent may be used alone, two or more kinds can also be used in combination.
[(F) crosslinking chemical]
The following describes crosslinking chemical.Crosslinking chemical can be enumerated as follows.
(i) by the aromatics of hydroxymethyl or alkoxy methyl replacement
The compound that (ii) has N-hydroxymethyl, N-alkoxy methyl or N-acyloxy methyl
(iii) epoxy compound
The following describes the compound of above-mentioned (i)-(iii).
The aromatics that is replaced by hydroxymethyl or alkoxy methyl of above-mentioned (i) for example can be enumerated by polysubstituted aromatics of methylol, acetoxy-methyl or alkoxy methyl or heterogeneous ring compound.Wherein, also comprise as the known resin-like compound that phenols and aldehyde condensation polymer are formed of resol.
In by methylol or polysubstituted aromatics of alkoxy methyl or heterogeneous ring compound, preferably with the hydroxyl adjoining position on have the compound of methylol or alkoxy methyl.
In addition, in polysubstituted aromatics of alkoxy methyl or heterogeneous ring compound, preferably the carbon number of alkoxy methyl is at the compound below 18, preferably by the compound of following general formula (1)-(4) expression.
Figure C0110430500371
General formula (1)
Figure C0110430500372
General formula (2)
Figure C0110430500381
General formula (3)
General formula (4)
In above-mentioned general formula (1)-(4), L 1-L 8Hydroxymethyl or the alkoxy methyl representing methoxy, ethoxyl methyl etc. respectively independently, replaced by 18 alkoxys below the carbon atom.
The cross-linking efficiency height of these crosslinking chemicals helps improving printability resistance.
Above-mentioned compound (ii) with N-hydroxymethyl, N-alkoxy methyl or N-acyloxy methyl, can enumerate monomer and oligomer-carbamide condensation product and the urea-formaldehyde condensation products put down in writing among EP-A-0133216, DE3634671, the DE3711264, the alkoxy substituted compound of putting down in writing among the EP-A-0212482.
Wherein, preferably for example has the carbamide derivant of 2 free N-hydroxymethyls, N-alkoxy methyl or N-acyloxy methyl at least, preferably N-(alkoxymethyl)-2 radical derivative.
Above-mentioned epoxy compound (iii) can be enumerated the epoxy compound of monomer with 1 above epoxy radicals, dipolymer, oligomer, polymkeric substance shape.Resultant of reaction of the resultant of reaction of bisphenol-A and epichlorhydrin, low-molecular-weight phenol-formaldehyde resin and chloropropylene oxide etc. for example.
The epoxy resin that can enumerate record among US4026705, the GB1539192 in addition, uses.The compound that uses above-mentioned (i)-(iii) is during as crosslinking chemical, divides general assembly (TW) with respect to the solid shape of photographic layer, and its addition is 5-80% (weight).Preferably 10-75% (weight), preferably 20-70% (weight).
During above-mentioned addition less than 5% (weight), the photographic layer permanance of resulting image recording material reduces sometimes, and when surpassing 80% (weight), the stability during preservation reduces sometimes.
In the present invention, can also use the phenol derivatives of (IV) following general formula (5) expression as crosslinking chemical.
General formula (5)
In above-mentioned general formula (5), Ar 1Expression can have substituent aromatic hydrocarbon ring.
Consider that from the angle of easy acquisition raw material above-mentioned aromatic hydrocarbon ring is phenyl ring, naphthalene nucleus or anthracene nucleus preferably.In addition, the preferably following alkylthio group of the following alkoxy of the following alkyl of halogen atom, 12 carbon atoms, 12 carbon atoms, 12 carbon atoms, cyano group, nitro, trifluoromethyl etc. of its substituting group.
Wherein, consider Ar from the angle that can realize high photosensitivity 1Preferably do not have substituent phenyl ring, naphthalene nucleus or have the following alkylthio group of the following oxyl of the following alkyl of halogen atom, 6 carbon atoms, 6 carbon atoms, 6 carbon atoms or nitro as substituent phenyl ring or naphthalene nucleus.
[(G) buck soluble high-molecular compound]
The buck soluble high-molecular compound that can use in cross-linked layer in the present invention, can be enumerated polymkeric substance that has hydroxyaryl on novolac resin or the side chain etc.Described novolac resin can be enumerated the resin that phenols and aldehydes condensation are obtained.
Wherein, preferably for example: the novolac resin that obtains by phenol and formaldehyde, the novolac resin that obtains by metacresol and formaldehyde, the novolac resin that obtains by paracresol and formaldehyde, the novolac resin that obtains by orthoresol and formaldehyde, the novolac resin that obtains by octyl phenol and formaldehyde, by/novolac resin that cresols and formaldehyde are obtained, by phenol/cresols (between can being, right, adjacent or/right, between/neighbour, adjacent/in mixing any) potpourri and the novolac resin that obtains of formaldehyde, with phenol and paraformaldehyde is raw material, do not use catalyzer, the high-molecular-weight novolak resin that the ortho position combination rate that reaction obtains under air-tight state and high pressure is high etc.
Above-mentioned novolac resin can be suitably to select the novolac resin of 800-300000, number-average molecular weight 400-60000 from weight-average molecular weight according to application target.
In addition, also can be the polymkeric substance that has hydroxyaryl on the above-mentioned side chain, the hydroxyaryl in this polymkeric substance can be enumerated the aryl in conjunction with 1 above OH base.
Above-mentioned aryl for example can be enumerated phenyl, naphthyl, anthryl, phenanthryl etc., wherein, considers the preferential phenyl or naphthyl of selecting from easy acquisition with the angle of transitivity.
The polymkeric substance that has hydroxyaryl on operable in the present embodiment, the side chain for example can be enumerated any the polymkeric substance that contains by in the formation unit of following general formula (IX)-(XII) expression.But be not limited to these polymkeric substance among the present invention.
Figure C0110430500412
Figure C0110430500414
In above-mentioned general formula (IX)-(XII), R 11Expression hydrogen atom or methyl.R 12And R 13Can be identical, also can be different, expression hydrogen atom, halogen atom, 10 alkyl, 10 alkoxy or 10 aryloxy group that carbon atom is following that carbon atom is following that carbon atom is following.In addition, R 12 and R 13Also can form phenyl ring or cyclohexane ring in conjunction with, the ring that contracts.R 14The alkyl of the divalence that expression singly-bound or 20 carbon atoms are following.R 15The alkyl of the divalence that expression singly-bound or 20 carbon atoms are following.R 16Expression singly-bound or 10 bivalent hydrocanbon radicals that carbon atom is following.X 1Expression singly-bound, ehter bond, thioether bond, ester bond or amido link.P represents the integer of 1-4.Q and r represent the integer of 0-3 respectively independently.
About these alkali-soluble macromolecules, the spy that the inventor formerly submits to is willing to [0130] of flat 11-320997-detailed description of [0163] Duan Zhongyou.
Operable buck soluble high-molecular in the present embodiment can only use a kind, also can be used in combination more than 2 kinds.
Solid shape with respect to photographic layer is divided total amount, and the addition of buck soluble high-molecular is 5-95% (weight), preferably 10-95% (weight), preferably 20-90% (weight).
During the addition less than 5% (weight) of buck soluble resin, the permanance of recording layer has can deterioration, otherwise, when surpassing 95% (weight), can not form image sometimes.
In addition, the operable known recording materials of method of the present invention can be enumerated: the spy opens the minus image recording material of putting down in writing among the flat 8-276558 that contains phenol derivatives; The minus recording materials of putting down in writing among the Te Kaiping 7-306528 that contain diazo-compounds; Put down in writing among the Te Kaiping 10-203037, use have ring contain the heterocyclic radical of unsaturated link polymkeric substance, utilize acid catalyst to carry out the minus Image forming material etc. of cross-linking reaction.The recording layer of putting down in writing in these documents can be applicable among the present invention the sour cross-linked layer as the negative photosensitive layer.
The following describes the positive type light sensitive layer.In the positive type light sensitive layer, will cut off as the key in the macromolecular compound of bonding agent by light or heat, perhaps remove the interaction between macromolecule, thereby improve dissolubility for the alkali imaging liquid.Such binder polymer can be enumerated the homopolymer that contains acidic groups on high molecular main chain and/or side chain, their multipolymer or their potpourri.
Wherein, consider, preferentially select the polymkeric substance that in high molecular main chain and/or side chain, has acidic groups that lists in following (1)-(6) from the angle that dissolubility and dissolving for alkaline imaging liquid suppress energy.
(1) phenylol (Ar-OH)
(2) sulfoamido (SO 2NH-R)
(3) substituted sulfonamides is acidic group (hereinafter to be referred as " active imino group ") [SO 2NHCOR ,-SO 2NHSO 2R ,-CONHSO 2R]
(4) carboxylic acid group (CO 2H)
(5) sulfonic group (SO 3H)
(6) phosphate (OPO 3H 2)
In above-mentioned (1)-(6), Ar represents to have substituent divalent aryl concatenating group, and R represents to have substituent alkyl.
In having the buck soluble high-molecular that is selected from the acidic groups in above-mentioned (1)-(6), preferentially select for use have (1) phenylol, the buck soluble high-molecular of (2) sulfoamido and (3) active imino group, from for dissolubility, the video picture tolerance of alkaline imaging liquid with guarantee that fully the angle of film strength considers, especially preferentially select buck soluble high-molecular for use with (1) phenylol or (2) sulfoamido.
Buck soluble high-molecular with the acidic groups that is selected from above-mentioned (1)-(6) for example can be enumerated as follows.
(1) the buck soluble high-molecular with phenylol for example can be enumerated: the condensed polymer of the condensed polymer of the condensed polymer of phenol and formaldehyde, metacresol and formaldehyde, paracresol and formaldehyde ,/to condensed polymer, phenol and the cresols of cresols and formaldehyde (, to or/in the potpourri any) with the condensed polymer of novolac resin such as the condensed polymer of formaldehyde and pyrogallol and acetone.Can enumerate the multipolymer that the compound copolymerization that has phenylol on the side chain is obtained in addition.The multipolymer that perhaps can also use the compound copolymerization that has phenylol on the side chain to obtain.
Compound with phenylol can be enumerated: acrylamide, Methacrylamide, acrylate, methacrylate or hydroxy styrenes etc. with phenylol.
Consider that from the angle of image formation property the weight-average molecular weight of buck soluble high-molecular is 5.0 * 10 2-2.0 * 10 4Be advisable, number-average molecular weight is 2.0 * 10 2-1.0 * 10 4Be advisable.In addition, these macromolecules not only may be used alone, two or more kinds can also be used in combination.In the occasion that is used in combination, also can and have the condensed polymer of the alkyl of 3-8 carbon atom as substituent phenol and formaldehyde with the condensed polymer of tert-butyl phenol of putting down in writing among the US4123279 and formaldehyde or the condensed polymer of octyl phenol and formaldehyde etc.
(2) have the buck soluble high-molecular of sulfoamido, for example can enumerate with the minimum that gets by compound and constitute the polymkeric substance that the unit constitutes as the main composition composition with sulfoamido.Such compound can enumerate have respectively in the molecule more than 1 on nitrogen-atoms at least in conjunction with the sulfoamido of 1 hydrogen atom and the compound of polymerisable unsaturated group.Wherein, preferably has the low molecular compound of acryloyl group, allyl or ethyleneoxy and replacement or single substituted-amino sulfonyl or substituted sulphonyl imino group in the molecule, for example the compound of 1.-5. representing by following general formula.
General formula 1.
Figure C0110430500442
General formula 2.
Figure C0110430500443
General formula 3.
General formula 4.
General formula 5.
In the above-mentioned general formula, X 1And X 2Respectively independently expression-O-or-NR 27-.R 21And R 24Represent independently respectively hydrogen atom or-CH 3R 22, R 25, R 29, R 32And R 36Represent to have alkylidene, ring alkylidene, arlydene or the inferior aralkyl of a substituent 1-12 carbon atom respectively independently.R 23, R 27And R 33Represent hydrogen atom, the alkyl that can have a substituent 1-12 carbon atom, naphthenic base, aryl or aralkyl respectively independently.In addition, R 26, R 27Represent to have alkyl, naphthenic base, aryl, the aralkyl of a substituent 1-12 carbon atom respectively independently.R 28, R 30And R 34Represent independently respectively hydrogen atom or-CH 3R 31, R 35Represent singly-bound respectively independently or can have a substituent 1-12 carbon atom alkylidene, the ring alkylidene, arlydene or inferior aralkyl.Y 3And Y 4Represent independently respectively singly-bound or-CO-.
In the compound that 1.-5. above-mentioned general formula is represented; for material, can preferentially select amino-sulfonyl phenyl methyl acrylate, N-(to the amino-sulfonyl phenyl) Methacrylamide, N-(to the amino-sulfonyl phenyl) acrylamide etc. between use for eurymeric lithography of the present invention.
(3) having the buck soluble high-molecular of active imino group, for example can enumerate and constitute the polymkeric substance that the unit constitutes as the main composition composition with the minimum that gets by compound with active imino group. such compound can be enumerated the change house thing that has the active imino group represented by following structural more than 1 and unsaturated group that can polymerization in the molecule respectively.
Figure C0110430500451
Specifically, can use N-(p-toluenesulfonyl) Methacrylamide, N-(p-toluenesulfonyl) acrylamide etc.
(4) have carboxylic acid group's buck soluble high-molecular, the minimum that for example can enumerate to be got by the compound that has 1 above carboxylic acid group and unsaturated group that can polymerization in the molecule respectively constitutes the polymkeric substance of unit as the main composition composition.
(5) have sulfonic buck soluble high-molecular, the minimum that for example can enumerate to be got by the compound that has 1 above sulfonic group and unsaturated group that can polymerization in the molecule respectively constitutes the polymkeric substance of unit as the main composition unit.
(6) have the buck soluble high-molecular of phosphate, the minimum that for example can enumerate to be got by the compound that has 1 above phosphate and unsaturated group that can polymerization in the molecule respectively constitutes the polymkeric substance of unit as the main composition unit.
The minimum buck soluble high-molecular, that have the acidic groups that is selected from above-mentioned (1)-(6) that is configured for the eurymeric Image forming material constitutes the unit, not necessarily be a kind, also can use minimum formation unit that will have same acidic groups more than 2 kinds or the minimum that has different acidic groups more than 2 kinds to constitute the product of unit copolymerization.
The method of copolymerization can be used known in the past grafting copolymerization process, segment copolymerization method, random copolymerization method etc.
Above-mentioned multipolymer, having of copolymerization are selected from the content of compound in multipolymer of the acidic groups of (1)-(6) and are advisable more than 10% (mole), preferably more than 20% (mole).When being lower than 10% (mole), often can not fully improve the video picture tolerance.
The infrared absorbent that can in the positive type light sensitive layer, use, (video picture of unexposed portion is suppressed must to produce positive interaction by the interaction with the binder polymer with particular functional base, exposure portion is disengaged, promotes video picture), consider from this point, especially preferentially select the infrared absorbent of salt type structure for use, specifically, in the operable infrared absorbent of the occasion of above-mentioned eurymeric, especially preferentially select cyanine dye and pyralium salt for use.The details of cyanine dye and pyralium salt is described hereinbefore.
In addition, can also use the anionic property infrared absorbent of putting down in writing among the special flat 10-237634 of hope.This anionic property infrared absorbent is meant, do not have cationic structural basically in the parent nucleus that absorbs ultrared pigment, has the infrared absorbent of anion structure.
For example can enumerate (a-1) anionic property metal complex, (a-2) anionic property carbon black, (a-3) anionic property phthalocyanine.
Infrared absorbent has the ability that absorbed infrared ray is transformed into heat, at this moment, in the recording materials of minus, generate acid or free radical owing to producing heat, crosslinked or polyreaction takes place in photographic layer, solidify the back and form image portion, in addition, in the recording materials of eurymeric, the heat that produces owing to laser scanning or because the effect of trimmed book body causes chemical reaction etc., the key in the polymkeric substance dissolves, exposure portion increases greatly for the dissolubility of imaging liquid, be removed through video picture, form non-image portion.
In these photographic layers, can also be according to application target also with above-mentioned known adjuvant.
In manufacture method of the present invention, in order on support, to form photographic layer, be dissolved in the solvent as long as will contain the photosensitive composite of mentioned component, be applied to then on the aluminium sheet of support.Described solvent can be used alone or as a mixture that the spy opens clear 62-251739, the spy opens the organic solvent described in the flat 6-242597.
The solid shape of photosensitive composite with 2-50% (weight) divided the concentration dissolving, disperseed, be coated on the support, carry out drying then.
The coating weight of the photosensitive composite layer (photographic layer) that is coated with on support in general, is calculated at 0.3-4.0g/m with dried weight according to purposes and different 2Be advisable.Along with coating weight reduces, can reduce to be used to obtain the exposure of image, but film strength reduces.Along with coating weight increases, must increase exposure, but the increase of sensitization film strength for example when being used as galley, can obtain printing high (the high anti-printing) galley of number.
Can add the surfactant, particularly fluorine that are used to improve the coating image quality in photosensitive composite is surfactant.
When making original edition of lithographic printing plate, at first the either party in the photosensitive composite layer on the back coating at the coating back side and surface on support also can both be coated with simultaneously.
The mode of photosensitive coated layer and condition can adopt the mode and the condition of many known photosensitive coated layers.That is, can adopt method, the method for using the extrusion type coating machine of using coating rod or the method for using the slip pearl etc.In addition, the condition of coating and coating fluid rerum natura can be to select various condition according to the coating weight of photographic layer and the rerum natura of photosensitive composite.
Below several method is elaborated.
Fig. 7 is the figure of an example of the apparatus for coating of coating photosensitive composite among expression the present invention, in Fig. 7, and the 506th, Wound-rotor type drawdown rod or notch-cut type drawdown rod, it and the sheet metal 504 equidirectional rotations of moving continuously.The 507th, excellent support unit is provided with on the whole length of rod 506, produces deflection to prevent rod 506, also has effect from the liquid feeder of coating fluid 503 to rod 506 that supply with simultaneously.Promptly, coating fluid 503 by be arranged on feeding mouth 508 on the excellent support unit 507 be fed into and weir piece 509 between in the feeding guiding ditch 510 that forms, rod by means of rotation moves up, be coated on the sheet metal 504, at this moment, on the contact site of sheet metal 504 and rod 506, carry out the metering of coating fluid 503, have only desirable coating weight to be coated on the sheet metal 504, remaining flows down, and forms hydrops 511 with the coating fluid 503 of new supply.Therefore, in the normal state, coating fluid 503 is applied on the sheet metal 504 by hydrops 511.When on sheet metal 504, being coated with coating fluid 503 by hydrops 511 like this, find that unexpectedly the superficiality of filming increased than in the past.And, because rod 506 has simultaneously coating fluid is transferred to the coating function on the sheet metal and measured the function that reaches desirable coating liquid measure, thereby device is very compact on the whole, not only can effectively utilize the space, and the operation of the setting of various conditions has been more prone to also.
In this mode, coating weight is that the groove size by the drawdown rod surface, the linear dimension of Wound-rotor type drawdown rod that promptly coiling forms on rod are controlled, thereby the range of control of coating weight is not accurate especially, normally 3-100ml/m 2
The diameter of drawdown rod has no particular limits, and adopts 3-20mm usually, and the rotation of drawdown rod can be and the same direction of sheet metal, also can be the direction opposite with it, and coating speed is the 10-150m/ branch.
As for the masking liquid rerum natura, viscosity is 0.7-500cp at shear rate 100l/ below second, viscosity is 0.7-300cp in shear rate 100-100000l/ second, preferably, at 100l/ is 0.7-100cp below second, is 0.7-60cp in 100-100000l/ second, and surface tension is 20-70dyn/cm, 25-50dyn/cm preferably, proportion is 0.8-1.5.
Can also adopt another kind of method, that is, by the squash type impregnator coating fluid that spues, to form coating fluid on the support that moves on the carrying roller crosslinked being wound on, and makes the crosslinked back decompression of coating fluid or its anterior pressurization is coated with.
In this mode, depend on the gap length on sheet metal and impregnator top, can be with 10-500cc/m 2Coating weight be coated with.
The condition optimization of coating fluid be, below second, be 0.7-60cp at shear rate 100l/ at 100-100000,0.7-100cp, surface tension is 20-50dyn/cm, proportion is 0.8-1.2.
In addition, 0.1-0.5mm is adopted in the gap of sheet metal and impregnator usually.
The following describes dry mode and condition.
Drying mode has following several: in the spy drives the drying device described in the flat 6-63487, dispose transfer roller, utilize these transfer roller transferring metal thin plates, with nozzle above sheet metal and below air supply, sheet metal is floated carry out dry mode; Do not use hot blast, use various media to be heated to high temperature, utilize its radiation heat to carry out dry mode; And use various media that roller is heated, contact the heat conduction that produces with sheet metal by roller and carry out dry mode.
Explain the mode of using heated-air drying below.
Fig. 8 is the constructed profile of an example of the drying device in the past that uses among the present invention of expression.Aluminium sheet 621 by guide roller R guiding, the continuous length that moves by the coating part 622 applied coating fluids that contain solvent, is imported in the 1st grade of dry section 623 then.In the 1st grade of dry section 623, be provided with to gas port 625 and exhausr port 626.By giving gas port 625 with 40 ℃-130 ℃, the hot blast of dew point-5～15 ℃ supply, through cowling panel 629 rectifications, with the wind speed of 0.5-4m/ second with contact through the above-mentioned film coated surface that forms on the aluminium sheet 621 that is coated on, make this dried coating film, then by exhausr port 626 discharges.Near the filming of aluminium sheet 621 of outlet that arrives the 1st grade of dry section 623 is the mantle state.Subsequently, the long aluminium sheet 621 that be directed to roller R guiding, moves continuously is imported in the 2nd grade of dry section 624.In the 2nd grade of dry section 624, be provided with to gas port 627 and exhausr port 628.By the hot blast of 60 ℃～150 ℃ that give that gas port 627 supplies with, dew point 5-20 ℃ by in the narrow slit type nozzle 630 with the 5-15m/ wind speed ejection of second, contact with the coated surface of aluminium sheet 621 is fierce, make the solvent evaporation in filming, the sclerosis of filming.Discharge by exhausr port 628 with the gas of filming after contacting.
As narrow slit type nozzle, common service condition is: nozzle gap, top 0.2-8mm, spacing 30-300mm, between nozzle and the sheet metal apart from 5-200mm.
On the photographic layer surface of above-mentioned setting, time that vacuumizes when using the vacuum printing frame contact exposure and prevent from unglazed rough layer to be set burn-back in order to shorten.Specifically, can enumerate the spy and open the method for putting down in writing among clear 50-125805, special public clear 57-6582, the special public clear 61-28986 that unglazed rough layer is set, and the method that makes the pressed powder heat fusion described in the special public clear 62-62337 etc.
In addition, as required, on the back side of the support of the original edition of lithographic printing plate that obtains with manufacture method of the present invention, the coating (back coating) that constitutes by organic high molecular compound of photographic layer damage in the time of can being provided for preventing to stack.Described organic polymer can be enumerated glass temperature at the saturated copolymer polyester resin more than 20 ℃, phenoxy resin, tygon (base) acetal resin and vinylidene chloride copolymer resins etc.
In addition, about each the structure of one deck only has been described more than the photographic layer, but the photographic layer that can be suitable in the inventive method is not limited thereto, and also can use the photographic layer of known sandwich construction, for example: by physics video picture stratum nucleare and the two-layer photographic layer that constitutes of silver halide emulsion layer; The photographic layer that layer that contains the polymer layer that is made of multi-functional monomer and multi-functional bonding agent, is made of silver halide layer and reductive agent and oxygen shielding layer are 3 layers; Comprise layer that contains linear phenol-aldehyde resin and naphthoquinone two azide and the two-layer photographic layer of layer that contains silver halide; The photographic layers of the layer 2-3 that is made of the laser absorption layer that can remove by laser radiation and lipophilicity layer and/or hydrophilic layer etc. can also be provided with the photographic layer that contains organic light-guide electricity body in addition.
The beneficial effect of the invention
Adopt the manufacture method of original edition of lithographic printing plate of the present invention, can with high throughput rate stably make good with aluminium sheet as support, laser explosure adaptability, improve with the adhesion of photographic layer thereby the original edition for lithographic printing plate of certain quality that the stability of little site portion and thin thread part and printability resistance are good.
The description of the drawings
Fig. 1 is that expression uses brush to carry out the synoptic diagram of an example of mechanical surface roughening treatment operation.In Fig. 1,101 expression aluminium sheets, 102 expression brush rolls, 103 expression abrasive pastes.
To be expression carry out the synoptic diagram of an example of the operation that chemical corrosion handles to the aluminium surface to Fig. 2.In Fig. 2,201 expression niprolls, 202 expression transfer rollers, 203 expression sprayers, 204 expression liquid-feeding pumps, liquid bath is transferred in 205 expressions, 211 expression corrosion treatment grooves, 222 expression aluminium sheets.
Fig. 3 is the operation of electrolytic surface roughening treatment is carried out in expression to aluminum support by the 1st and the 2nd electrolytic surface roughening treatment the synoptic diagram of an example.In Fig. 3,301 expression aluminium sheets, 302 expressions the 1st surface coarsening device, 303 expressions the 2nd surface coarsening device, 304 expression back side alligatoring devices, the main electricity level of 306 expressions, 307 expression cylinders, 308 expression electrolytic solution.
Fig. 4 is the operation of anodized is carried out in expression to surface of aluminum plate the synoptic diagram of an example.401 expression anodized devices in Fig. 4, electric groove is given in 412 expressions, 414 electrolytic treatments grooves, 416 expression aluminium sheets, 418 and 426 expression electrolytic solution, 430-1 represents the 1st section electrolysis electrode, 430-2 represents the 2nd section electrolysis electrode, and 430-3 represents the 3rd section electrolysis electrode, and 434-1 represents the 1st section direct supply, 434-2 represents the 2nd section direct supply, and 434-3 represents the 3rd section direct supply.
Fig. 5 is the synoptic diagram of an example of the method for the expression Rmax (maximum height) that obtains aluminium base, in Fig. 5, and 504 expression aluminium sheets, 503 expression coating fluids, 511 expression hydrops.
Fig. 6 is the synoptic diagram of an example of the method for the expression Rp (depth of centre line) that obtains aluminium base.In Fig. 6,621 expression aluminium sheets, 622 expression coating parts, 623 and 624 expression dry sections, gas port is given in 625 expressions, 626 expression exhausr ports.
Fig. 7 is the synoptic diagram that is illustrated in an example of the painting process that is coated with coating fluid (photographic layer) on the aluminium sheet.
Fig. 8 is an example of dry drying process is carried out in expression to the aluminium sheet with the coating coating fluid a synoptic diagram.
The preferred forms (embodiment) of invention
Explain the present invention below by embodiment, but the invention is not restricted to these embodiment.
Embodiment 1-4
[manufacturing of support]
Use the device of Fig. 1,, change rotating speed and pressure in good time, control Ra (surfaceness), Rp (depth of centre line) and Rmax (maximum height), aluminium (JIS 1050) is made the substrate of various levels with the abrasive material of average 30 μ m.Then, use the device of Fig. 2, concentration sodium hydroxide is kept 15% constant, under 50 ℃ of temperature, handle,, make under various conditions in order to control the value of a30.Not homogenizing processing is carried out with salpeter solution in the washing back, uses the device of Fig. 3 then, adopts nitric acid 1%, Al 0.5%, 45 ℃ of temperature and spy to open the power supply wave shape described in the flat 3-79799, at 50c/dm 2-700c/dm 2Scope change electric weight, with the device of Fig. 2, naoh concentration is kept 10%, at 0.1g/m 2-1g/m 2Between corrode, make the different sample of difference in surface area.Then, using the device of Fig. 4, is 3g/m according to the oxide film amount 2Control electric weight, and temperature is controlled at 50 ℃, proportion and conductivity are controlled at certain value, the flow velocity between the Al of groove 414 plate and electrode is divided into the 1st section to the 3rd section, changes various conditions shown in the according to the form below.Condition when resulting physics value shown in the table 1 and generation anode oxide film.
Table 1
a30 (％) Surface area (%) Ra (μm) Rp (μm) Rmax (μm) Anode oxide film process flow rate (cm/ second) The 1st section current density (A/dm 2) The 2nd section current density (A/dm 2) The 3rd section current density (A/dm 2)
Embodiment 1 35 28 0.55 3.5 4.8 25 10 20 30
Embodiment 2 50 45 0.35 2.2 3.0 2 10 15 40
Embodiment 3 60 65 0.70 5.1 6.5 220 5 20 30
Embodiment 4 15 17 0.22 1.6 2.1 40 15 20 30
For embodiment 1-4, as the following photographic layer of photographic layer use separately.
[photosensitive layer coating liquid (a)]
Carbon black dispersion liquid 10g
4-diazonium diphenylamine and formaldehyde condensation products
Phosphorus hexafluoride hydrochlorate 0.5g
The free-radical polymerized thing of methacrylic acid, acrylic acid (2-hydroxyethyl) ester, methacrylic acid benzyl ester, vinyl cyanide, mol ratio 15: 30: 40: 15, weight-average molecular weight 100,000 5g
Malic acid 0.05g
FC-430 (fluorine that Minnesota Mining and Manufacturing Company makes is a surfactant)
0.05g
1-methoxyl-2-propyl alcohol 80g
Lactate 15g
Water 5g
[photosensitive layer coating liquid (b)]
Capric acid 0.03g
Specific multipolymer (with resin, have the monomer of sulfoamido and have in the monomer of active imino group at least a kind and contain the above multipolymer of 10% (mole)) 0.75g as copolymer composition with phenolic hydroxyl
Between, paracresol linear phenol-aldehyde resin (/ contrast=6/4)
0.25g
P-toluenesulfonic acid 0.003g
Tetrahydrophthalic anhydride 0.03g
Cyanine dye 0.017g
It is the anionic dyestuff of 1-naphthalene sulfonic aicd that Victoria's ethereal blue makes the counterion of BOH
0.017g
Megafac F-177 (surfactant, big Japanese ink chemical industrial company makes) 0.05g
Gamma-butyrolacton 10g
Methylethyl 10g
1-methoxyl-2-propyl alcohol 1g
[photosensitive layer coating liquid (c)]
Capric acid 0.03g
Between, paracresol linear phenol-aldehyde resin (/ contrast=6/4)
1g
P-toluenesulfonic acid 0.003g
Tetrahydrophthalic anhydride 0.03g
Cyanine dye 0.017g
It is the anionic dyestuff 0.017g of 1-naphthalene sulfonic aicd that Victoria's ethereal blue makes the counterion of BOH
Megafac F-177 (surfactant, big Japanese ink chemical industrial company makes) 0.05g
Gamma-butyrolacton 10g
Methyl ethyl ketone 10g
1-methoxyl-2-propyl alcohol 1g
[photosensitive layer coating liquid (d)]
Photopolymerization layer sensitization liquid
Tetramethylol methane tetraacrylate 1.5g
Linear organic high molecular polymer (B1) 2.0g
Sensitizer (C1) 0.15g
(λmaxTHF479nm、ε＝6.9×104)
Light trigger (D1) 0.2g
IRGACURE907 (E1) (manufacturing of Ciba-Geigy company) 0.4g
ε-phthalocyanine/(B1) disperses thing 0.2g
Fluorine is non-ionic surfactant Megafac F177
(big Japanese ink chemical industry (strain) is made) 0.03g
Methyl ethyl ketone 9g
Propylene glycol methyl ether acetate 7.5g
Toluene 11g
The oxygen shielding layer
Polyvinyl alcohol (PVA)
3% (weight) aqueous solution of (saponification degree 98% (mole), the degree of polymerization 500)
[photosensitive layer coating liquid (e)]
The polymer layer coating fluid
Tetramethylol methane tetraacrylate 2.5g
20% (weight) propylene glycol monomethyl ether solution 37.5g of allyl methacrylate/methacrylic acid copolymer (copolymerization is than 80/20)
Dispersible pigment dispersion 13.0g
Methyl ethyl ketone 74.0g
Photosensitive layer coating liquid (polymer layer coating dry back coating)
The polyvinyl alcohol (PVA) of saponification degree 79.5% (trade name: PVA-405,
Ku Lalei (Network ラ レ) (strain) manufacturing) 10% (weight) aqueous solution
10.5g
0.11% (weight) methanol solution of following additives (SH-1)
0.41g
0.11% (weight) aqueous solution of following additives (SH-2)
0.41g
Above-mentioned silver emulsion 0.50g
5% (weight) aqueous solution of surfactant (SA-1)
0.40g
Water 7.80g
Reductive agent dispersion liquid 1.20g
Oxygen shielding layer (in photosensitive coated layer and the coating of dry back)
The polyvinyl alcohol (PVA) of saponification degree 98.5% (trade name: PVA-105.
Ku Lalei (Network ラ レ) (strain) manufacturing) 10% (weight) aqueous solution
200.0g
Alkali precursor (following structure) dispersion liquid 1.25g
Water phase surfactant mixture 4.0g
Figure C0110430500551
Figure C0110430500552
Figure C0110430500553
(alkali precursor)
Figure C0110430500554
Figure C0110430500555
[photosensitive layer coating liquid (f)]
Resin bed
The naphthoquinones-1 of acetone-pyrogallol liquid resin, 2-two nitrine-(2)-5-
Sulphonic acid ester 5.0g
Cresol-formaldehyde resin 10.0g
Methyl ethyl ketone 150g
Cyclohexanone 122g
Photographic layer (coating resin layer and the coating of dry back)
Chlorine silver bromide gelatin emulsion (Cl:70% (mole), Br:30% (mole), mean grain size: the gelatin amount of 0.28 μ m, every 1kg emulsion: 55g, silver halide content: 0.85 mole) 1000g1,3-diethyl-5-[2-(3-(3-sulfopropyl) benzoxazoles-2-indenes) ethylidene] ocean current is because of 0.1% methanol solution of acid sodium-salt
50ml
4-hydroxyl-6-methyl isophthalic acid, 3,3a, 0.5% aqueous alkali 100ml of 7-tetrazine
2,2% aqueous solution of 4-two chloro-6-hydroxyl-s-triazines
35ml
[photosensitive layer coating liquid (g)]
Physics video picture stratum nucleare
Coating makes dry weight (silver amount) be 5mg/m with the silver sol of Carey Lea method preparation 2
Silver halide layer (being coated on the physics video picture stratum nucleare)
With 2.0g/m 2Amount coating by the bromide formation of the chloride and 60% (mole) of 40% (mole), average particle size is the chlorine silver bromide emulsion (silver salt: gelatin (weight ratio)=1: 1) of 0.3 μ m.
[photosensitive layer coating liquid (h)]
The optical conductive layer coating fluid
Fastogen Blue 8120
(big Japanese ink (strain) is made metal-free phthalocyanine 1.0 weight portions
The multipolymer of methyl methacrylate and methacrylic acid
(methacrylic acid 20% (mole)) 10.0 weight portions
Tetrahydrofuran 60 weight portions
Cyclohexanone 40 weight portions
Protective layer used coating fluid (on optical conductive layer, being coated with)
Polyvinyl butyral
(Deuki Kagaku Kogyo Co., Ltd makes, 2000-L)
2.0 weight portion
Stearic acid 0.5 weight portion
Ethanol 97.5 weight portions
[photosensitive layer coating liquid (i)]
Has the macromolecular compound that produces the functional group of sulfonic acid by the effect of acid on the side chain
1.0g
(above-mentioned macromolecular compound can use the spy to open the compound of putting down in writing among the flat 10-20706g)
Adjacent benzoquinones diazido-4-sulfonic acid chloride 0.1g
Make the counterion of Victoria's pure blue B OH become the dyestuff of 1-naphthalene-sulfonic acid
0.05g
Fluorine is surfactant (Megafac F-176PF, big Japanese ink chemical industry (strain) is made) 0.06g
Methyl ethyl ketone 10g
Gamma-butyrolacton 10g
[photosensitive layer coating liquid (j)]
According to opening the photographic layer that film that method same described in the flat 11-139023 is made, silver-colored exposes with the spy
Comparative example 1
With the device of Fig. 1, use similarly to Example 1 the JIS1050 material and the abrasive material of average 30 μ m, change rotating speed and extrusion pressure in good time, control Ra, Rp and Rmax make various levels.Then, use the device of Fig. 2, concentration sodium hydroxide is 15%, handles under 50 ℃ of temperature, in order to control the a30 value, makes under various conditions.Not homogenizing processing is carried out with salpeter solution in the washing back, uses the device of Fig. 3 then, opens the condition described in the flat 3-79799 by the spy and uses nitric acid 1%, Al 0.5%, 45 ℃ of temperature and power supply wave shape, at 50c/dm 2-700c/dm 2Scope in change electric weight, use the device of Fig. 2, naoh concentration is set at 10%, at 0.1g/m 2-1g/m 2Between corrode, make the different sample of difference in surface area.Then, use the device of Fig. 4, according to making the oxide film amount reach 3g/m 2The control electric weight is not controlled temperature, proportion and conductivity, changes the condition of the Al thin plate of groove 414 and the flow velocity between the electrode and the 1st section to the 3rd section shown in the according to the form below.Condition when resulting physics value shown in the table 2 and generation anode oxide film.The same photographic layer that uses among formation and the front embodiment 1-4.
Table 2
a30 (％) Surface area (%) Ra (μm) Rp (μm) Rmax (μm) Anode oxide film process flow rate (cm/ second) The 1st section current density (A/dm 2) The 2nd section current density (A/dm 2) The 3rd section current density (A/dm 2)
Comparative example 1 35 28 0.55 3.5 4.8 25 10 20 30
Comparative example 2-10
Use the device of Fig. 1 and the abrasive material of average 30 μ m, change rotating speed and extrusion pressure in good time, control Ra, Rp and Rmax make the JIS1050 material with the same various levels of the foregoing description 1.Then, use the device of Fig. 2, concentration sodium hydroxide is 15%, handles under 50 ℃ of temperature, in order to control the a30 value, makes under various conditions.Not homogenizing processing is carried out with salpeter solution in the washing back, uses the device of Fig. 3 then, opens the condition described in the flat 3-79799 by the spy and uses nitric acid 1%, A1 0.5%, 45 ℃ of temperature and power supply wave shape, at 50c/dm 2-700c/dm 2Scope in change electric weight, use the device of Fig. 2, naoh concentration is set at 10%, at 0.1g/m 2-1g/m 2Between corrode, make the different sample of difference in surface area.Then, use the device of Fig. 4, according to making the oxide film amount reach 3g/m 2The control electric weight is controlled at 50 ℃ with temperature, and proportion and conductivity are controlled to be certain value, changes the condition of the Al thin plate of groove 414 and the flow velocity between the electrode and the 1st section to the 3rd section shown in the according to the form below.Condition when resulting physics value shown in the table 3 and generation anode oxide film.The same photographic layer that uses among formation and the front embodiment 1-4.
Table 3
a30 (％) Surface area (%) Ra (μm) Rp (μm) Rmax (μm) Anode oxide film process flow rate (cm/ second) The 1st section current density (A/dm 2) The 2nd section current density (A/dm 2) The 3rd section current density (A/dm 2)
Comparative example 2 75 32 0.55 3.5 4.8 25 10 20 30
Comparative example 3 40 9 0.35 2.2 3.0 2 10 15 40
Comparative example 4 60 65 0.95 5.1 6.5 200 5 20 30
Comparative example 5 15 17 0.22 2.0 2.9 35 15 20 30
Comparative example 6 35 28 0.55 3.5 4.8 0.5 5 20 30
Comparative example 7 35 28 0.55 3.5 4.8 260 5 20 30
Comparative example 8 50 45 0.35 2.2 3.0 100 10 10 10
Comparative example 9 60 65 0.70 5.1 6.5 50 20 20 20
Comparative example 10 15 17 0.22 1.6 2.1 60 30 30 30
[evaluation of printability resistance and image formation property]
Printing performances such as the printability resistance of the embodiment 1-4 that obtains more than the investigation, the original edition of lithographic printing plate of comparative example 1-10 and image formation property.Printability resistance is to estimate by the number of resulting good print product, and contaminative is to estimate by the reconstruction of image of the image portion of the resulting printed matter of visualization and the contaminative of non-image portion.
As a result, for embodiment, all support productivitys are good, obtain certain quality as original edition of lithographic printing plate, and when forming all photographic layers, printing performances such as the reconstruction of image of printability resistance, site and fine rule etc. and contaminative are all very good.
On the other hand, in the anodic oxidation membrane process of support, do not carry out the comparative example 1 of conductivity control, do not obtain the goods of certain quality, aluminium base characteristic before use forming anode oxide film exceeds in each comparative example outside the scope of the invention, comparative example 2 to be difficult for contaminative relatively poor, the printability resistance of comparative example 3 is inferior, non-image of comparative example 4 occurs polluting, contaminative is bad, residual film appears in comparative example 5 when low exposure, produce on comparative example 6 and 7 the support surface inhomogeneous, the epithelium also heterogeneity that distributes.In addition, in anode oxide film forms operation, each comparative example that current density is certain, the throughput rate of comparative example 8 is low, and comparative example 9 and 10 aluminium sheet edge part produce current concentration, do not make goods.

Claims (5)

1. the manufacture method of original edition of lithographic printing plate, it is characterized in that, adopt the mechanical surface alligatoring, in order to NaOH is that the liquid of main body corrodes and based at least 2 kinds of technologies in the electrolytic surface alligatoring of hydrochloric acid or nitric acid aluminium base carried out surface coarsening, perhaps surface coarsening and corrosion, the aluminium sheet of following requirement condition (1)-(4) is satisfied in manufacturing, use then with sulfuric acid, oxalic acid or phosphoric acid are the treating fluid of main body, the different district more than 3 sections of current density is set, and the conductivity of the treating fluid of each section is identical, wherein, the 1st section current density is at 0.1-15A/dm 2Scope, making the 1st section current density simultaneously is below 60% with respect to the current density of terminal section, the current density of the section between them is the current density between the current density of the 1st section current density and terminal section, electrolyte flow rate is in the 1-250cm/ scope of second, carry out anode oxide film and generate operation, obtain aluminum support, on this support, form the photographic layer that writes with infrared laser
(1) resolution of usage level direction is that the atomic force microscope of 1.9 μ m is measured in the square scope of 240 μ m, and the ratio of degree of tilt more than 30 degree is in 70%;
(2)0.15μm≤Ra≤0.90μm；
(3)Rp≤8Ra；
(4)Rmax≤14Ra，
Wherein, Ra presentation surface roughness; Rmax represents maximum height; Rp represents the degree of depth of center line.
2. the manufacture method of the described original edition of lithographic printing plate of claim 1 is characterized in that, the aluminum support that obtains through above-mentioned anode oxide film generation operation has the surface configuration that satisfies following condition (5),
(5) difference in surface area is more than 10%, below 90%,
Described difference in surface area, the resolution that is to use horizontal direction is the atomic force microscope of 0.1 μ m, measures surface configuration in the square scope of 50 μ m, establishing the surface area of obtaining with approximate 3 methods is a 1, the top projected area is a 0The time, with % unit representation [(a 1-a 0)/a 0] value of * 100.
3. the manufacture method of the described original edition of lithographic printing plate of claim 1 is characterized in that, generates in the operation at described anode oxide film, and liquid temperature, conductivity and the proportion of the treating fluid of each section all is identical separately.
4. the manufacture method of the described original edition of lithographic printing plate of claim 1, it is characterized in that described photographic layer is to contain infrared absorbent, produces the compound of acid or free radical and by the sour and crosslinked compound or the negative photosensitive layer of free-radical polymerised compound by heat.
5. the manufacture method of the described original edition of lithographic printing plate of claim 1 is characterized in that, described photographic layer be contain infrared absorbent, the acidic compound and have positive type light sensitive layer by heat by the compound of the acid joint portion of decomposing.
CN 01104305 2000-02-24 2001-02-23 Producing method for lithographic printing plate originals Expired - Fee Related CN1237394C (en)

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US7029820B2 (en) 2001-10-05 2006-04-18 Fuji Photo Film Co., Ltd. Support for lithographic printing plate and presensitized plate and method of producing lithographic printing plate
JP5014782B2 (en) * 2006-12-28 2012-08-29 三菱アルミニウム株式会社 Method for producing surface-treated aluminum material and apparatus for producing surface-treated aluminum material
JP5073287B2 (en) * 2006-12-28 2012-11-14 三菱アルミニウム株式会社 Method for producing surface-treated aluminum material and apparatus for producing surface-treated aluminum material
JP5014781B2 (en) * 2006-12-28 2012-08-29 三菱アルミニウム株式会社 Method for producing surface-treated aluminum material and apparatus for producing surface-treated aluminum material
JP5401026B2 (en) * 2007-09-26 2014-01-29 富士フイルム株式会社 Resin composition for laser engraving, resin printing plate precursor for laser engraving, relief printing plate and method for producing relief printing plate
CN101293441B (en) * 2008-06-23 2010-04-14 石深泉 Environment-friendly ink-jet CTP offset master and production method thereof
US20100173135A1 (en) * 2009-01-06 2010-07-08 Jonghan Choi Method of Controlling Surface Roughness of a Flexographic Printing Plate
TWI405040B (en) * 2010-10-01 2013-08-11 Chi Mei Corp A positive-type photosensitive resin composition, and a method of forming a pattern
TWI435176B (en) * 2011-06-22 2014-04-21 Chi Mei Corp Positive photosensitive resin composition and method for forming patterns by using the same
KR101193571B1 (en) * 2011-12-23 2012-10-25 (주)아인스 Electrolyte for coating a film on aluminum and method for coating a film on aluminum using thereof
CN105818563A (en) * 2015-01-05 2016-08-03 中国科学院化学研究所 Offset plate base surface treatment method
CN107663108A (en) * 2016-07-29 2018-02-06 比亚迪股份有限公司 Ceramic coarsening solution and preparation method thereof and ceramic method of roughening
KR102658153B1 (en) * 2017-09-28 2024-04-16 제이에스알 가부시끼가이샤 Radiation-sensitive resin composition and use thereof
CN108983551A (en) * 2018-08-22 2018-12-11 南京中电熊猫液晶材料科技有限公司 Coating machine photo resistance recovery system
JP6693629B1 (en) * 2019-05-27 2020-05-13 ナトコ株式会社 Water-based coating composition for topcoat of metal siding, method for producing metal siding, and water-based coating composition for topcoat of metal siding

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