CN1511712A

CN1511712A - Original edition of lithographic printing plate

Info

Publication number: CN1511712A
Application number: CNA2003101242442A
Authority: CN
Inventors: 堀田久
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2002-12-27
Filing date: 2003-12-29
Publication date: 2004-07-14
Anticipated expiration: 2023-12-29
Also published as: JP3787334B2; JP2004249693A; CN1323852C

Abstract

To provide an original plate for a planographic printing plate, which is excellent in any of sensitivity, and printing resistance, scumming resistance and easy viewability of a water rise in the use of the original plate as the planographic printing plate. In this original plate for the planographic printing plate, an image recording layer, where an image can be formed by heat, is provided on a substrate for the planographic printing plate, which is obtained by applying electrochemical surface roughing using an aqueous solution containing at least hydrochloric acid, anodic oxidation and alkaline-metal silicate treatment to an aluminum plate. The substrate for the planographic printing plate has a grained surface with a structure wherein a large pit with an average opening diameter of 2-10 [mu]m and a small pit with an average opening diameter of 0.05-0.8 [mu]m are superposed on each other, and the average ratio of the depth of the small pit to the opening diameter thereof is in a range of 0.2-0.6. In terms of the substrate for the planographic printing plate, a surface area difference [Delta]S<SP>50</SP>, which is obtained by means of an atomic force microscope, is in a range of 20-40%, and the coating weight of Si atoms on the surface of the substrate for the planographic printing plate is in a range of 1.0-12.0 mg/m<SP>2</SP>. (C)2004,JPO&NCIPI.

Description

Original edition of lithographic printing plate

Technical field

The present invention relates to original edition of lithographic printing plate.

Background technology

Lithography is a kind of water and oil mode of printing of not miscible principle in fact that utilizes, wherein on the printing surface of the lithographic plate that is used, can form and hydrophilicly scold the zone (is non-image part to call this zone in the following text) of printing ink and scold the zone of water oleophylic China ink that (to call this zone in the following text is image section.)。

Used aluminium base support (the following support body for lithographic plate printing plate that only claims in the lithographic plate.), because making non-image part, its surface uses, so requiring has good hydrophily and water-retaining property, in addition, also requiring has good cohesive etc. with the image recording layer that is provided with in the above, and promptly support must possess above-mentioned various opposite performance.

If the hydrophily of support is low excessively, non-image part will be adhered to printing ink when then printing, and cylinder dressing (blanket) can be contaminated, and then can produce so-called scum.In addition, if the water-retaining property of support is too poor, do not have abundant damping medicine moisture during then as if printing, space of a whole page shade (shadow) part will blockage phenomenon.Thereby the water width of cloth can narrow down.

On the other hand,,, preferably make the concaveconvex shape on surface mild, to avoid adhering to of unnecessary printing ink for the character that keeps be difficult for polluting in non-image part.But if make the concavo-convex shape on surface mild, then the cohesive of image recording layer and support will descend, anti-seal reduction.It is the relation that resistance to soiling and Nai Yin have compromise selection.

In order to make the support of these well behaved lithographic printing plate-uses, generally be sand screen mesh to be carried out on the surface of aluminium plate handle (asperities processing), give that it is concavo-convex.About this concavo-convex various scheme that proposed.

For example, disclose following lithographic plate in patent documentation 1, promptly support has the dual structure of big or small hole (pit), and big hole has uniformity, and that the average pore size of little hole is 0.2 μ m is above, below the 0.8 μ m, and the ratio in the degree of depth of little hole and aperture is below 0.2 μ m.

But this lithographic plate exists the poor adhesion between image recording layer and the support, the problem that anti-seal is low.

In addition, in general, lithographic plate can make by original edition of lithographic printing plate is exposed and develops, and when exposure that suits and development, the speed of original edition of lithographic printing plate is important characteristic.

To improve speed etc. is purpose, following scheme has been proposed in the patent documentation 2, promptly contain benzoquinones two repeatedly in the lithographic plate of the specific photosensitive layer of nitrilo compound and triaizine compounds having, difference in surface area, mean roughness and the brightness that expresses support for the concavo-convex level index in surface is defined in the specific scope.

But,, then have the problem of speed difference if the image recording layer that can be formed image by the effect of heat is set on the used support of this lithographic plate.

In addition, in the printing of using lithographic plate, can the detect by an unaided eye bright situation of the non-image part on the space of a whole page of operator is regulated the balance of the amount of printing ink and dumping processing solution.Therefore, observe the complexity of bright situation, promptly observe the complexity of the shinny state of the so-called space of a whole page (shininess ofthe plate surface), become the key property of lithographic plate.

Like this, for original edition of lithographic printing plate, wish that it has excellent performance in speed and aspect the complexity of anti-seal, stain resistance and the shinny state of the observation space of a whole page when making lithographic plate and using.But the original edition of lithographic printing plate that these characteristics are all excellent is not still known.

Yet people know, as the means of the anti-seal that improves lithographic plate, can (handle to call roasting version in the following text by the back heat treated after developing.) image recording layer is solidified.And known, with the novolac resin key component as handling the image recording layer that anti-seal is increased substantially by roasting version.

But having with this novolac resin is the original edition of lithographic printing plate of the image recording layer of key component, is difficult to regulate the balance between speed and stain resistance and the Nai Yin.

Therefore, wait in expectation speed and the anti-seal when making lithographic plate, resistance to soiling and observe the performances such as complexity of the shinny state of the space of a whole page all excellent, the preferably appearance of the original edition of lithographic printing plate of the anti-seal after roasting version is handled (to call " the anti-seal of roasting version " in the following text).

Patent documentation 1

Te Kaiping 11-99758 communique

Patent documentation 2

Te Kaiping 8-123014 communique

Summary of the invention

The original edition of lithographic printing plate that also has the good anti-seal of the roasting version excellent performances such as complexity of the anti-seal when the purpose of this invention is to provide a kind of speed and making lithographic plate, resistance to soiling and the shinny state of the observation space of a whole page, preferred.

For achieving the above object, when present inventors found to be controlled at the adhesion amount that the Si atom is gone up on the surface configuration of support body for lithographic plate printing plate and surface in the particular range, the performances such as complexity of speed and anti-seal, resistance to soiling and the shinny state of the observation space of a whole page when making lithographic plate were all excellent.

In addition, inventors also find, if use the support of above-mentioned lithographic printing plate-use, even under using with the situation of novolac resin as the image recording layer of key component, also can reach balance between speed and resistance to soiling, the anti-seal, handle the effect that anti-seal also may obtain to increase substantially through roasting version.

Have again, inventors also find, if use the support of above-mentioned lithographic printing plate-use,, can reach balance between speed and resistance to soiling, the anti-brush even in fact do not contain alkali silicate and contain under the situation of developing liquid developing of PH9.0-13.5 of non-reducing sugar and alkali using.In addition,, can prevent the generation of impurity and mud when then developing, so can improve the stability of developer solution significantly if use this developer solution.

Inventors have finished the present invention based on these opinions.

Promptly the present invention proposes the scheme of following (1)-(3).

(1) a kind of master of lithographic plate, it is the master that support body for lithographic plate printing plate is provided with the lithographic plate that image recording layer that effect by heat can form image forms, and the support of this lithographic printing plate-use uses the processing of electrochemistry asperities, anodized and the alkali silicate processing that contain aqueous solution of hydrochloric acid at least to make to aluminium sheet

Described support body for lithographic plate printing plate have from the teeth outwards by average pore size be 2-10 μ m big hole peace all the aperture be the overlapping Grains shape and structure that forms of little hole of 0.05-0.8 μ m, and, mean value with respect to the ratio of the degree of depth in aperture, described pitting cave is 0.2-0.6

For the support of described lithographic printing plate-use,, measure surperficial 50 μ m with active force microscope between atom ²Square frame in 512 * 512 points obtain three-dimensional data, and try to achieve real area S according to approximate line-of-sight course by this three-dimensional data _x ⁵⁰, again by real area S _x ⁵⁰The area S of Ce Dinging geometrically _o ⁵⁰, try to achieve difference in surface area △ S by following formula (1) ⁵⁰Be 20-40%,

The adhesion amount of Si atom is 1.0-15.0mg/m on the surface of described support body for lithographic plate printing plate ²

△S ⁵⁰＝(S _x ⁵⁰-S _o ⁵⁰)/S _o ⁵⁰×100(％)????????????????(1)

(2) original edition of lithographic printing plate of being put down in writing in above-mentioned (1), wherein said image recording layer contain the above novolac resin of 30 quality %.

(3) a kind of preparation method of lithographic plate, wherein, after original edition of lithographic printing plate described in above-mentioned (1) or (2) exposed, the pH that contains non-reducing sugar and alkali with in fact not containing alkali silicate was that the developer solution of 9.0-13.5 develops, and obtains lithographic plate.

Description of drawings

Fig. 1 is the side schematic view of used brush granulation (brush graining) operation in the mechanical asperities processing during support body for lithographic plate printing plate among expression preparation the present invention.

Fig. 2 is the profile of an example of the electrolysis asperities treating apparatus that has plane alternating current electrolysis groove that uses when making used support body for lithographic plate printing plate among the present invention of expression.

Fig. 3 is the profile of another example of the electrolysis asperities treating apparatus that has plane alternating current electrolysis groove that uses when making used support body for lithographic plate printing plate among the present invention of expression.

Fig. 4 is the profile of an example of the electrolysis asperities treating apparatus that has radial pattern alternating current electrolysis groove that uses when making used support body for lithographic plate printing plate among the present invention of expression.

Fig. 5 is the alternately figure of an example of waveform current waveform figure that expression is used for the processing of electrochemistry asperities when making used support body for lithographic plate printing plate among the present invention.Among the figure, 2,20-alternating current electrolysis groove, 4A, 4B, 4C, 26A, the 26B-main pole, 6A, 6B, 14A, the 14B-transfer roller, 8A, the 16A-guide-in roller, 8B, the 16B-outlet roller, 10, the 34-auxiliary electrolytic cell, 12, the 36-auxiliary electrode, 22-alternating current electrolysis groove body, the 22A-opening portion, 24-transfer roller, 28A, 28B-feed flow nozzle, 30A-upstream side deflector roll, 30B-downstream deflector roll, 32-overflow launder, the bottom surface of 34A-auxiliary electrolytic cell, 35-upstream side guide roller, 51-aluminium alloy plate, 52,54-roller shape brush, the 53-grinding milk, 55,56,57, the 58-backing roll, 100,102,104-electrolysis asperities treating apparatus, the a-direction of transfer, the T-transmission plane, T _Ac-power supply, Th1, Th2, Th3, Th4, Th5-silicon controlled rectifier (SCR) (thyristor), W-aluminium strip, the ta-anode reaction time, the tb-cathode reaction time, the peak point current of the time Ia-anodic cycle side of tc-electric current, the peak point current of Ic-cathode deposition period side from zero to peak value.

The specific embodiment

Introduce the present invention below in detail.

[support of lithographic printing plate-use]

The support of the lithographic printing plate-use that adopts among the present invention have from the teeth outwards by average pore size be 2-10 μ m big hole peace all the aperture be the overlapping Grains shape that constitutes of little hole of 0.05-0.8 μ m, and, be 0.2-0.6 with respect to the mean value of the ratio of the degree of depth in aperture, described pitting cave.

With active force microscope between atom, interior 512 * 512 points of square frame of measuring surperficial 50 μ m obtain three-dimensional data, and try to achieve real area S by this three-dimensional data according to approximate line-of-sight course _x ⁵⁰, again by real area S _x ⁵⁰The area S of Ce Dinging geometrically _o ⁵⁰, the difference in surface area △ S that tries to achieve by following formula (1) ⁵⁰Be 20-40%,

The adhesion amount of Si atom is 1.0-15.0mg/m on the surface ²

△S ⁵⁰＝(S _x ⁵⁰-S _o ⁵⁰)/S _o ⁵⁰×100(％)??????????????(1)

(lip-deep Grains shape)

Be than darker concavo-convex of the thickness of the moisture film of fountain solution because average pore size is the big hole of 2-10 μ m,, just can with the naked eye judge the amount of the fountain solution that gives the space of a whole page when then printing at an easy rate if therefore have big hole on the surface of support.The performance of promptly observing the complexity of the shinny state of the space of a whole page becomes good.Thereby, the amount of just regulating the fountain solution of supplying with the space of a whole page easily.If there is not big hole, then because concavo-convex few, so the fountain solution surface is just more level and smooth, the performance of observing the complexity of the shinny state of the space of a whole page will variation.The average pore size of big hole also is like this when too small.If the average pore size of big hole is excessive, then will to reach balance just very difficult for speed, anti-seal and resistance to soiling.The average pore size of big hole is more than 2 μ m, more than the preferred 4 μ m, and below 10 μ m, preferably below 8 μ m.

Average pore size is the little hole of 0.05-0.8 μ m, mainly is to keep image recording layer by tackify (fixing) effect, has the function of giving anti-seal.If the average pore size of little hole is excessive, the quantity that then plays the hole boundary member of viscosifying action will reduce, so make anti-seal reduction sometimes.In addition, average pore size is that the little hole of 0.05-0.8 μ m also can be brought into play the effect that forms uniform moisture film, improvement resistance to soiling.The average pore size of little hole is more than the 0.05 μ m, is preferably more than the 0.1 μ m, and below 0.8 μ m, is preferably below the 0.6 μ m.

In the present invention, be 0.2-0.6 with respect to the mean value of the ratio of the degree of depth in aperture, pitting cave, can obtain good anti-seal and resistance to soiling thus.If the mean value with respect to the ratio of the degree of depth in aperture, pitting cave is too little, then its anti-seal is relatively poor sometimes.Mean value with respect to the ratio of the degree of depth in aperture, pitting cave is more than 0.2, to be preferably more than 0.3, and below 0.6, preferably below 0.5.

In the present invention on the support body for lithographic plate printing plate of Cai Yonging, the average pore size of the big hole on surface, the average pore size of little hole, and the standard deviation in aperture, pitting cave and as described below with respect to the assay method of the mean value of the degree of depth in aperture.

(1) average pore size of big hole

With SEM with 1000 times multiplying power from directly over take the surface of support, in gained SEM photo, extract out 50 holes around be linked to be the big hole of ring-type, read its diameter and establish and do the aperture, calculate average pore size again.

(2) average pore size of little hole

With the multiplying power of high-resolution SEM with 50000 times, from directly over take the surface of support, in gained SEM photo, extract 50 little holes out, read its diameter and establish and do the aperture, calculate average pore size again.

(3) average with respect to the ratio of the degree of depth in aperture, pitting cave

Average with respect to the ratio of the degree of depth in aperture, pitting cave, be that 20 apertures of extraction are the little hole below the 0.8 μ m in the SEM photo that makes, and read the aperture and the degree of depth with the cross section of high-resolution SEM with 50000 times multiplying power shooting support, ask its ratio, calculate mean value again.

In addition, in the support body for lithographic plate printing plate that adopts among the present invention,, try to achieve real area S according to approximate line-of-sight course by the three-dimensional data that obtains with 512 * 512 points in the square frame of active force measurement microscope surface 50 μ m between atom _x ⁵⁰, again by real area S _x ⁵⁰The area S of Ce Dinging geometrically _o ⁵⁰, the difference in surface area △ S that tries to achieve by above-mentioned formula (1) ⁵⁰Be 20-40%.

△ S ⁵⁰Expression is through the real area S of asperities processing _x ⁵⁰The area S that measures on the relative geometry _o ⁵⁰The factor of increase degree.If △ is S ⁵⁰Become big, then the contact area with image recording layer just becomes big, and the result can make anti-seal raising.In order to make △ S ⁵⁰Become big, effectively be provided with a large amount of this little concavo-convex from the teeth outwards.As a large amount of this little concavo-convex methods is set from the teeth outwards, suitable enumerate as: use with hydrochloric acid do the electrolyte of main component the processing of electrolysis asperities, use the electrolysis asperities processing of making the electrolyte of main component with the nitric acid of high concentration and high temperature.By mechanical asperities processing method or use general nitric acid to do the electrolysis asperities processing of the electrolyte of main component, also can make △ S ⁵⁰Become big, but its asperities degree is little.

Among the present invention, △ S ⁵⁰Be more than 20%, to be preferably more than 25%.If, △ S ⁵⁰Excessive, then resistance to soiling can descend, so △ S ⁵⁰Below 40%, preferably below 35%.

On support body for lithographic plate printing plate of the present invention, as asking for △ S ⁵⁰Method, as described below.

(1) mensuration of the microscopical surface configuration of active force between the usefulness atom

Among the present invention, in order to ask for △ S ⁵⁰, measure surface configuration with active force microscope (Atomic ForceMicroscope:AFM) between atom, try to achieve three-dimensional data.

Mensuration can be carried out under the following conditions.Promptly, support body for lithographic plate printing plate is cut into the foursquare size of 1cm, be placed on the horizontal sample platform of piezoelectric scanning instrument, make cantilever near sample surfaces, when in the scope that arrives active force generation effect between atom, in the enterprising line scanning of XY direction, at this moment can obtain the concavo-convex of sample from the displacement of piezoelectricity on the Z direction.The piezoelectric scanning instrument can use that sweep limits is 150 μ m on the XY direction, is the scanner of 10 μ m on the Z direction.The resonant frequency of cantilever is that 120-150kHz, spring constant are device (SI-DF20, the セイコ one イ Application ス Star Le メ Application Star) corporate system of 12-20N/m; NCH-10, NANOSENSORS corporate system; Or AC-160TS, Olympus Corp's system), (Dynamic Force Mode) measures with the DFM type.In addition, by the three-dimensional data of trying to achieve being similar to the small inclination of least square correcting sample, try to achieve datum level.

During measurement, measure interior 512 * 512 points of square frame of the last 50 μ m in surface.Resolution ratio on the XY direction is that the resolution ratio on 1.9 μ m, the Z direction is that 1nm, sweep speed were 60 μ m/ seconds.

(2) △ S ⁵⁰Calculating

(f (x, y)), and extract three adjacent points out asks the small leg-of-mutton area summation that is formed by these three points, as real area △ S with the three-dimensional data of trying to achieve in above-mentioned (1) ⁵⁰, difference in surface area △ S ⁵⁰According to the real area S that records _x ⁵⁰The area S of Ce Dinging geometrically _o ⁵⁰, try to achieve by above-mentioned (1) formula.

Also have, in the support of the lithographic printing plate-use that adopts among the present invention, the adhesion amount of the Si atom on surface is 1.0-15.0mg/m ²

The adhesion amount of Si atom is meant with fluorescent x-ray analyzer (XRF:X-ray FluorescenceSpectrometer), by the quality of Si atom on the per unit area of calibration curve method mensuration.If the adhesion amount of Si atom very little, then speed and resistance to soiling are just relatively poor sometimes, in addition, if too many, then can cause anti-seal poor.

Among the present invention, the adhesion amount of Si atom is 1.0mg/m ²More than, that better is 3.0mg/m ²More than, and at 15.0mg/m ²Below, preferably at 10.0mg/m ²Below.When aluminium sheet contains the Si atomic time, above-mentioned numerical value is the data of replenishing after the amount of contained Si atom.

As the production standard curve and the standard sample of usefulness, can with as the sodium silicate aqueous solution that will contain the Si atom of known quantity make its dry aluminium sheet after dropping in the 30mm φ area on the aluminium sheet equably.The condition example of x-ray fluorescence analysis is as follows.

Fluorescent x-ray analyzer: electric machine industry corporate system RIX 3000 of science, X-ray tube ball: Rh, mensuration spectrum: Si-K α, tube voltage: 50kV, tube current: 50mA, slit: COARSE, beam split crystallization: RX4, detector: F-PC, analysis area: 30mm φ, peak position (2 θ): 144.75deg, background (background) (2 θ): 140.70deg and 146.85deg, cumulative time: 80 seconds/sampling.

(aluminium sheet (calendering aluminium))

The aluminium sheet that adopts among the present invention, can be from pure aluminum plate, with aluminium containing of main component micro-xenogenesis element alloy sheets or the plastic sheeting of lamination or AM aluminum metallization select.Contained micro-xenogenesis element is more than one the element of selecting in institute's column element from the periodic table of elements in the aluminium sheet, and its content is 0.001-1.5 quality %.

As the exemplary of xenogenesis element contained in the aluminium alloy, can enumerate as silicon, iron, nickel, manganese, copper, magnesium, chromium, zinc, bismuth, titanium, vanadium.Usually use the material known of record in the aluminium handbook the 4th edition (1990, light metal association), for example: JIS A1050 material, JIS A3005 material, JIS A1100 material, JIS A3004 material, international registration alloy 3103A or added the alloy of the magnesium below the 5 quality % in order to improve hot strength therein.

In addition, the aluminium sheet that uses among the present invention also can be to roll the aluminium sheet that makes to taking the base bullion that contains many impurity that beverage can etc. regenerates apart.

In manufacture method described later,, still,, also can obtain uniform Grains shape (cellular hole) by in aqueous hydrochloric acid solution, carrying out electrochemical asperities processing even above-mentioned content of elements is more.

Among the present invention, also can use save from the DC casting that intermediate annealing is handled and/or all heat treatment and the aluminium sheet made, save from continuous casting process that intermediate annealing is handled and the aluminium sheet made.

The thickness of aluminium sheet is good with 0.05-0.8mm, with 0.1-0.6mm for better.

In the preparation of support body for lithographic plate printing plate of the present invention, preferably above-mentioned aluminium sheet is included in the electrochemistry asperities processing that contains in the aqueous solution of hydrochloric acid and makes support body for lithographic plate printing plate in interior surface treatment, in this surface treatment, also can comprise various processing, in addition, in the various operations that the present invention adopts, because the alloying component of used aluminium sheet can be eluted in the treatment fluid used in its operation, so, the alloying component that can contain aluminium sheet in the treatment fluid, these alloying components of interpolation before handling particularly make treatment fluid be in stable state and use to well.

In the present invention, though the various treatment process combinations of aftermentioned can be carried out the asperities processing,, before the processing of various electrochemistry asperities, to carry out that alkaline etching is handled or decontamination is treated to goodly, also preferably handle in addition and the order of decontamination processing is handled by alkaline etching.Secondly, after the processing of various electrochemistry asperities, alkaline etching is handled or decontamination is treated to carry out, and also preferably handles by the order that alkaline etching is handled and decontamination is handled.Have, the alkaline etching after the processing of various electrochemistry asperities is handled and also can be omitted again.

Among the present invention, also preferably before handling, these carry out mechanical asperities processing.Various electrochemical asperities processing also can be carried out more than 2 times.In addition, after these treatment process, also can seal processing, hydrophilicity-imparting treatment etc.

Particularly carrying out surface treatment by the order of the electrochemistry asperities processing in alkaline etching processing, decontamination processing, the aqueous hydrochloric acid solution, alkaline etching processing and/or decontamination processing, anodized, hydrophilicity-imparting treatment is one of perfect condition of the present invention.

At this moment, be one of perfect condition of the present invention with alkali silicate in the hydrophilicity-imparting treatment.In addition, at this moment, before initial alkaline etching was handled, surface treatment comprised that mechanical asperities processing is one of desirable state of the present invention.

Be elaborated respectively with regard to mechanical asperities processing, alkaline etching processing, decontamination processing, the processing of electrochemistry asperities, anodized, sealing processing and hydrophilicity-imparting treatment below.

(mechanical asperities processing)

Among the present invention, mechanical asperities processing is to carry out to good before the processing of electrochemistry asperities.By mechanical asperities processing, the surface area of aluminium sheet will increase.

Before with brush granulation aluminium sheet, at first as required, can be used to remove the ungrease treatment of surperficial rolling oil, such as ungrease treatment with interfacial agent, organic solvent or aqueous alkali etc.But adhering to after a little while of rolling oil can be saved ungrease treatment.

Then, with a kind or at least 2 kinds of different brushes of mao footpath, the limit provides grinding milk to surface of aluminum plate, and the brush granulation is carried out on the limit.

About mechanical asperities processing, the spy opens in flat 6-135175 communique, the special public clear 50-40047 communique and is documented.In this brush granulation, the brush that begins usefulness claims the 1st brush, the brush of usefulness claims the 2nd brush at last.Among Fig. 1,51 expression aluminium sheets, 52 and 54 expression roller shape brushes, 53 expression grinding milks, 55,56,57 and 58 expression backing rolls.As shown in Figure 1, preferably, during granulation, clamp

brush

52 and 54 and two backing rolls 55,56 and 57,58 that aluminium sheet 51 disposes the roller shape respectively.Two backing rolls 55,56 and 57,58 be configured to its each other the beeline on surface the external diameter than

roller shape brush

52 and 54 is also little respectively, aluminium sheet 51 is to be exerted pressure by

roller shape brush

52 and 54 and to squeeze under the state between 2 backing rolls 55,56 and 57,58, be transmitted with certain speed, and, grinding milk 53 is supplied with surface of aluminum plate, by the rotation of roller shape brush, lapped face.

The brush that adopts among the present invention it is desirable to be used in the base material portion of roller shape with even staple length and plants the distribute brush of brush material such as implanting a nylon, polypropylene, animal wool, steel wire of hair; In roller shape platform portion, open aperture and implant the brush of brush pieces; The brush of with groove roller (channel roller) type etc.Wherein, desirable material is a nylon, and planting a mao back desirable staple length is 10-200mm.That implants on the brush roll plants gross density with every 1cm ²Implant the 30-1000 root and be, better be the 50-300 root.

The desirable hair footpath of this brush be 0.24-0.83mm, better be 0.295-0.72mm.The section shape of hair is good with circle.If the hair footpath is littler than 0.24mm, then the resistance to soiling of dash area is understood variation, and if bigger than 0.83mm, then the resistance to soiling on cylinder dressing can variation.The material of hair is good with nylon, though nylon 6, nylon 66, NYLON610 etc. are all available, and, the dimensional stability that causes from hot strength, wear resistance, suction, bending strength, hear resistance, aspect such as restorative consider, most preferably NYLON610.

Brush number, desirable is more than 1 10 below, better is more than 16 below.The brush roller such as the spy open in the flat 6-135175 communique record, also can combine by the different brush roller in hair footpath.

Secondly, the rotating speed of brush roller can be at 100rpm at random selecting between the 500rpm.Backing roll uses has rubber or metal surface and the linear material of the fine maintenance of energy.The direction of rotation of brush roller is advisable along the direction that transmits aluminium sheet as shown in Figure 1.The brush roller has when several, and the counter-rotating of part brush roller also can.The amount of being pressed into of brush is controlled by the load of the rotation drive motor of brush, and the electrical power of rotation drive motor consumption is controlled at 1.0-15kW for well, and 2-10kW is then better.

Among the present invention, carry out the asperities processing with above-mentioned thick brush after, handle with thin brush again, can get the support that hydrophily, water-retaining property and cohesive all have both, therefore preferred.At this moment, fountain solution dash area after a little while can not be damaged, so the water fabric width, be difficult for to produce scum, and then can not influence the cohesive with image recording layer yet.

The grinding milk that uses among the present invention preferably is distributed to the slurries of gained in the water with average grain diameters such as silica sand, aluminium hydroxide, alumina powder, volcanic ash, float stone, carborundum, diamond dust as the grinding agent of 1-50 μ m (desirable be 20-45 μ m), and the specific gravity control of these slurries is in the scope of 1.05-1.3.Average grain diameter is meant the volume with respect to whole grinding agents contained in the slurries, and when getting the cumulative frequency of particle proportion of various diameters, the accumulation ratio accounts for 50% particle diameter.

In addition, handling center line average roughness (Ra) to the mechanical asperities processing reaches 0.3-1.0 μ m and is advisable.

The surface configuration that certainly, also can adopt mode, the mode that adopts metal plug of spraying slurries, will have the stack of jog is transferred to the mode on the aluminium sheet etc.As other mode, open the spy that clear 55-074898 communique, spy are opened clear 61-162351 communique, the spy opens in clear 63-104889 communique etc. on the books.

After as mentioned above aluminium sheet being carried out the brush granulation, then, chemical etching is carried out for well in the surface of aluminium sheet.This chemical etching is handled has effects such as removing the grinding agent that is absorbed in the surface of aluminum plate of brush granulated processed, aluminium bits, and simultaneously, the electrochemistry asperities processing of carrying out after also making it reaches more even and better effect.

(chemical etching in the aqueous alkali is handled)

It is etched by above-mentioned aluminium sheet being contacted with aqueous slkali carry out that alkaline etching is handled.When not carrying out mechanical asperities processing, rolling oil, dirt, autoxidation film that alkaline etching is handled to remove described aluminium sheet (calendering aluminium) surface are purpose, carry out under the situation of mechanical asperities processing, so that the arris dissolving of the jog that generates through mechanical asperities processing, to make the surface with smooth bent face be purpose.

As the method that aluminium sheet is contacted with aqueous slkali, can enumerate method as making aluminium sheet impregnated in method in the groove that aqueous slkali is housed by the method in the groove that aqueous slkali is housed, with aluminium sheet, aqueous slkali is sprayed to surface of aluminum plate.

This method for chemially etching be presented in United States Patent (USP) the 3rd, 834 in detail, in No. 398 specifications.If more specifically describe, be immersed in can dissolved aluminum solution in, the method for more specifically saying so and in aqueous alkali, soaking.

Comprise NaOH, potassium hydroxide, tertiary sodium phosphate, tripotassium phosphate, sodium aluminate, sodium metasilicate, sodium carbonate etc. as above-mentioned alkali.If the use aqueous alkali, etching speed is very fast.

With the aqueous solution of the 0.05-40 quality % of these alkali, under 40 ℃-100 ℃ liquid temperature, handle 5-300 and be advisable second during chemical etching.The concentration of aqueous alkali for well, can contain the alloying component that is contained that comprises aluminium component of 0-10 quality % with 1-30 quality % in aluminium alloy.As aqueous alkali, preferred especially NaOH is the aqueous solution of main component.It is preferred handling 1-120 second under normal temperature-95 ℃ liquid temperature.

After the etch processes operation finishes, for fear of bringing treatment fluid into next procedure, be advisable to come mangle with roll and to wash with sprayer.

The chemical etching amount of aluminium sheet, with the meltage of one-sided aluminium sheet at 0.001-30g/m ²For good, 1-15g/m more preferably ², be preferably 3-12g/m especially ²

(acid etching processing)

Acid etching is handled and is meant the processing of aluminium sheet being carried out chemical etching in acidic aqueous solution, and is suitable in the laggard behavior of above-mentioned electrochemistry asperities processing.In addition, before the processing of above-mentioned electrochemistry asperities and/or afterwards, carry out above-mentioned alkaline etching when handling, handle carrying out also can carrying out acid etching again after alkaline etching is handled.

Aluminium sheet is carried out handling if carry out above-mentioned acid etching after above-mentioned alkaline etching handles, then can remove silica containing interphase of surface of aluminum plate or simple substance Si, can overcome the defective of the anode oxide film that in anodized thereafter, generates.The problem of adhering to the point-like printing ink that is known as dust shape dirt when its result can prevent to print in non-image part.

Used acidic aqueous solution in handling as acid etching can be enumerated and contain phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid or the aqueous solution of the nitration mixture more than 2 kinds in them.Wherein, be preferred with the aqueous sulfuric acid.The concentration of acidic aqueous solution with 50-500g/J for well.Can contain alloying component contained in the aluminium sheet that comprises aluminium component in the acidic aqueous solution.

Liquid temperature when acid etching is handled is 60-90 ℃, is preferably in 70-80 ℃ and handles 1-10 second.The meltage of aluminium sheet at this moment is with 0.001-0.2g/m ²For good.In addition, acid concentration, as sulfuric acid concentration and aluminium ion concentration, do not separate out at normal temperatures be chosen as in the scope of crystallization suitable.Desirable aluminium ion concentration is 0.1-50g/L, and that desirable especially is 5-15g/L.

In addition, after finishing acid etching and handling,, it is desirable to roll treatment fluid and aluminium sheet is washed by sprayer by roll for fear of treatment fluid is taken in the next procedure.

((the 1st decontamination processing) handled in the decontamination in the acidic aqueous solution)

If carry out chemical etching, in general, handle so at this moment carry out decontamination with the nitration mixture that contains phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid or the acid more than 2 kinds in them owing to can generate dirt on the surface of aluminium sheet with aqueous alkali.The concentration of acidic aqueous solution is advisable with 0.5-60 quality %.In the acidic aqueous solution also solubilized contained alloying component in the aluminium alloy that comprises aluminium component of 0-5 quality % is arranged.

In addition, especially preferably use the waste liquid that produces in the waste liquid that produces in the processing of electrochemistry asperities, the anodized as the treatment fluid of decontamination.

The liquid temperature is a normal temperature to 95 ℃, is preferably 30-70 ℃ especially.Processing time with 1-120 second for well, be preferably 1-5 second especially.After the decontamination processing finishes,, it is desirable to roll treatment fluid and wash by sprayer by roll for fear of treatment fluid is taken in the next procedure.Solutions employed is a solution of the same race or during with the solution of same composition in decontamination treatment fluid and the following operation, just can omit the operation of being rolled treatment fluid and being washed with sprayer by roll.

In the device of electrochemistry asperities processing usefulness, when using the impressed current anode groove for the dissolving that prevents electrode and control asperities shape, if being placed in by indirect current on the aluminium sheet, the impressed current anode groove carries out then also can saving the decontamination operation in the acidic aqueous solution before the processing of electrochemistry asperities before the groove of electrochemistry asperities processing.

(processing of electrochemistry asperities)

Electrochemistry asperities of the present invention processing is characterised in that, carries out the processing of electrochemistry asperities in saliferous aqueous acid (following also title " is the aqueous solution of key component with hydrochloric acid ").

By processing of electrochemistry asperities and the anodized under these specified conditions, carry out hydrophilicity-imparting treatment, mechanical asperities processing as required, promptly the various surface treatments by introducing in the present disclosure just can reach purpose of the present invention.

In addition, electrochemical asperities processing also can be carried out repeatedly, carries out in the aqueous solution that with described hydrochloric acid is key component before or after the processing of electrochemistry asperities, also can carry out electrochemical asperities processing in the aqueous solution that with nitric acid is key component.

Below, be illustrated with regard to electrochemical asperities processing.

(1) with hydrochloric acid is the aqueous solution of key component

Said among the present invention is the aqueous solution of key component with hydrochloric acid, can use and common carry out aqueous solutions employed in the processing of electrochemistry asperities, can in the aqueous hydrochloric acid solution of 1-30g/L, add 1g/L has nitrate ion to saturated aluminum nitrate, sodium nitrate, ammonium nitrate etc. nitrate compound with direct current or alternating current; Aluminium chloride, sodium chloride, ammonium chloride etc. have more than one uses in the hydrochloric acid of salt acid ion.In addition, also can add the compound that forms complex with copper with the ratio of 1-200g/L.Being in the aqueous solution of key component with hydrochloric acid, also can be dissolved with metals such as iron contained in the aluminium alloy, copper, manganese, nickel, titanium, magnesium, silicon.Also can add hypochlorous acid or the hydrogen peroxide of 1-100g/L.

Aqueous hydrochloric acid solution is preferably in the liquid temperature especially in 15-50 ℃ the aqueous solution of hydrochloric acid that contains 1-30g/L, with ratio interpolation aluminium salt (aluminium chloride, the AlCl of 10-300g/L ₃6H ₂O) make aluminum ions concentration reach the aqueous solution of 1-30g/L.If use this aqueous hydrochloric acid solution to carry out electrochemical asperities processing, then the surface configuration through this asperities processing is even, even use the aluminium calendering plate (contain the aluminium sheet of many alloying components or do not regulate the aluminium sheet of alloying component) of low-purity, it is mottled also can not produce processing after this asperities processing, as the lithographic plate time spent, can have excellent anti-seal and printing performance (resistance to soiling) concurrently.

Here, aqueous hydrochloric acid solution is good with the hydrochloric acid that contains 5-20g/L, serves as special good to contain 8-15g/L.

The aluminum chloride hexahydrate that is added is preferably 10-300g/L, and more preferably 5-200g/L is preferably 80-150g/L especially.

Added in the aqueous hydrochloric acid solution of aluminum chloride hexahydrate, its aluminum ions concentration for well, is better with 5-20g/L with 1-30g/L, is special good with 8-15g/L.

As making an addition to hydrochloric acid is additive, device, power supply, current density, flow velocity, temperature in the aqueous solution of key component, can adopt the condition of using in the processing of known electrochemistry asperities.Though available alternating current of power supply or the direct current used in the processing of electrochemistry asperities are still, good with alternating current to serve as the spy.Carry out in the aqueous solution that with hydrochloric acid is key component in the electrochemical asperities processing, aluminium sheet participates in the electric weight of anode reaction, and the time point that finishes with the processing of electrochemistry asperities is as the criterion, can be at 10-1000C/dm ²Scope in select, with 200-800C/dm ²For preferably, with 300-600C/dm ²For preferred especially.

(2) with nitric acid be the aqueous solution of key component

Said among the present invention is the aqueous solution of key component with nitric acid, can use and common carry out aqueous solutions employed in the processing of electrochemistry asperities, can in the aqueous solution of nitric acid of 1-100g/L, add 1g/L has nitrate ion to saturated aluminum nitrate, sodium nitrate, ammonium nitrate etc. compound with direct current or alternating current; Aluminium chloride, sodium chloride, ammonium chloride etc. have the hydrochloric acid of salt acid ion or using more than a kind of nitrate compound.The ratio of all right 1-200g/L is added the compound that forms complex with copper.Be in the aqueous solution of main component with nitric acid, also solubilized has metals such as iron contained in the aluminium alloy, copper, manganese, nickel, titanium, magnesium, silicon.Also can add hypochlorous acid or the hydrogen peroxide of 1-100g/L.

Particularly preferably in the liquid temperature for 15-90 ℃, contain and add aluminium salt (aluminum nitrate) in the aqueous solution of 5-15g/L nitric acid, so that aluminium ion reaches the aqueous solution of 3-50g/L.As making an addition to nitric acid is material, device, power supply, current density, flow velocity, temperature in the aqueous solution of key component, can adopt the condition of using in the processing of known electrochemistry asperities.Though the available interchange of power supply or the direct current that use in the processing of electrochemistry asperities, with alternating current for preferred especially.In the electrochemical asperities processing in the aqueous solution that with nitric acid is key component, aluminium sheet participates in the electric weight of anode reaction, and the time point that finishes with the processing of electrochemistry asperities is as the criterion, can be at 10-1000C/dm ²Scope in select preferred 100-500C/dm ², preferred especially 150-300C/dm ²

(3) electrochemistry asperities processing

The processing of so-called electrochemistry asperities is meant in acidic aqueous solution, aluminium sheet and and its corresponding electrode between, perfectly straight stream or alternating current, the process of carrying out the processing of electrochemistry asperities.Among the present invention, preferred especially alternating current, no matter this alternating current is that single-phase, two-phase or three-phase electricity all can be used.Also can use the superimposed electric current of alternating current and direct current.

The electrolytic treatments groove with arbitrary known groove all can, the electrolytic cell that the electrolytic cell of using during the processing of electrochemistry asperities can be used with known surface treatments such as perpendicular type, plane, radial patterns.The electrolytic treatments groove also can be provided with a plurality of.In addition, establish under the condition of catholyte processing etc. of the aluminium sheet in etch processes in acid or the aqueous alkali, decontamination processing, acid or the neutral brine solution in the acidic aqueous solution at folder, electrochemical asperities processing also can be carried out repeatedly.

A) method of powering to aluminium sheet

Mode from the conductor roller to the mode of aluminium sheet power supply that can directly power with or the mode (indirect power supply mode) of powering without the liquid of conductor roller.Both can be parallel through the electrolyte in the electrolytic cell with the direction that aluminium sheet advances, also can be opposite.Can connect the AC power more than 1 on electrolytic cell.When adopting indirect power supply mode, preferably adopt the method for the use impressed current anode of putting down in writing in special fair 6-37716 communique, the special fair 5-42520 communique, the ratio of the electric weight when electric weight when regulating the anode that puts on aluminium sheet and negative electrode.The rectifier cell such as the most handy silicon controlled rectifier (SCR) of electric current, diode, GTO that flows through impressed current anode is controlled.If use the mode of putting down in writing in the special fair 6-37716 communique, the then just control easily of electric weight (current value) corresponding to as the electric weight carbon electrode of the main pole that carries out electrochemistry asperities processing reaction, on the surface of aluminum plate during anode of alternating current and negative electrode the time.In addition, on supply unit was made, the influence of the magnetic field skew of transformer is also little, and was highly beneficial on the cost.

When carrying out electrochemical asperities processing with sine wave, the control method of current value is dual-purpose transformer and type variable induced voltage regulator, is current value used in the electrolysis to be fed back in the type variable induced voltage regulator carry out.At this moment, in the method for control current value, such as the spy open in the clear 55-25381 communique record, but dual-purpose is with the method for silicon controlled rectifier (SCR) control phase.

In electrochemical asperities processing, if the flow velocity of the distance of aluminium sheet and electrode and liquid is not necessarily, the deviation of electric current just easily takes place, its result will form mottledly on the surface of aluminium sheet, produce the product of the support that is not suitable for doing lithographic printing plate-use.In order to address this problem, the width that can use inside to be provided with fluid reservoir and aluminium sheet is provided with the feed flow nozzle of the slit that the 1-5mm atomizing of liquids uses.In addition, a plurality of fluid reservoirs are set especially preferably, and respectively with pipe arrangement that fluid reservoir links to each other on valve and flowmeter are set, regulate respectively from the liquid measure of slit ejection.

The distance of aluminium sheet and electrode is 5-100mm, is preferably 8-15mm especially.For make this apart from keeping constant, can adopt put down in writing in the special public clear 61-30036 communique, the sliding surface of the plate that moves is added static pressure, plate is crimped on the mode that the state on the sliding surface moves.In addition, also can adopt as the spy open put down in writing in the flat 8-300843 communique, make electrode and aluminium sheet keep the method for certain distance with the big roller of diameter.

When adopting direct feeding system, preferably use as specially open the conductor roller of putting down in writing in the clear 58-177441 communique, and be used in the spy and open the device of putting down in writing in the clear 56-123400 communique and carry out the processing of electrochemistry asperities.The conductor roller can be arranged on the top of aluminium sheet or below, still, especially preferably be located at aluminium sheet above, be pressed on the aluminium sheet with clamping device.The length that aluminium sheet contacts with the conductor roller, the relative aluminium sheet direction of advancing, with 1-300mm for well.Clamp aluminium sheet with relative with the conductor roller to delivery roll, with rubber system roller for well.The pressure of pushing, the hardness of rubber rollers can be set arbitrarily under the condition that does not produce arc spot (arc spot).By the conductor roller is located at aluminium sheet above, can make the operation of changing conductor roller and examination become very convenient.Preferably adopt the mode that power supply brush and slip limit, rotary body limit are switched in the end of conductor roller.

On the conductor roller that is pressed on the aluminium sheet, in order to prevent to produce arc spot, the electrolyte that used electrolyte has same composition, a uniform temp in commonly used and the processing of electrochemistry asperities is cooled to.Owing in electrolyte, in case sneak into foreign material, just easily produce arc spot, so, in the sprayer of cooling usefulness, be involved in filter cloth, or in the pipe arrangement of injection spray pipe upstream side, put into the very thin filter of mesh for well.

B) the electrochemistry asperities processing of use alternating current

The waveform of the AC power of using in the processing of electrochemistry asperities can be used sine wave, square wave, trapezoidal wave, triangular wave etc., still, with square wave or trapezoidal wave for well, be best with trapezoidal wave.Frequency with 0.1-500Hz for well, with 40-120Hz serve as better, be best with 45-65Hz.

When using trapezoidal wave, the time tp of electric current when 0 reaches peak value for well, is best with 0.2-1.5msec with 0.1-2msec.Because the influence of the AC resistance of power circuit is so if tp less than 0.1 when then current waveform rises, just needs big supply voltage, the cost that power supply is provided with will be high.If bigger than 2msec, then be subjected to the influence of micro constitutent in the electrolyte easily, be difficult to carry out uniform asperities processing.The condition of the one-period of used alternating current is in the processing of electrochemistry asperities, the anode reaction time ta of aluminium sheet accounts for ratio (claiming " duty " among the present invention) ta/T of ac period T, for well, is better with 0.45-0.55 with 0.33-0.66, is best with 0.5.

During cathode reaction, having generated with aluminium hydroxide on the surface of aluminium sheet is the oxide-film of main component, and oxide-film can dissolved or destruction sometimes.Therefore, if dissolving takes place or destroys in oxide-film, the part of then dissolving and destroying, the place that the point-like corrosion reaction begins when just becoming the anode reaction of next aluminium sheet.Therefore, the selection of alternating current duty particular importance with regard to the angle of carrying out the processing of uniform electrolysis asperities.

Be applied to relative with mainboard to aluminium sheet on electric weight, the electric weight Q when being preferably the aluminium sheet cathode reaction _c, and the electric weight Q during anode reaction _aRatio Q _c/ Q _aIn the scope of 0.9-1.0, that desirable is 0.92-0.98, and optimal is 0.94-0.96.If Q _c/ Q _aIn this scope, what then the asperities processing caused mottledly just can not produce, and when making lithographic plate and using, just can have anti-seal and printing performance (resistance to soiling) concurrently.In addition, if Q _c/ Q _aSurpass 1.0, electrode will dissolve sometimes.Just can this electricity ratio by regulating by the voltage that power supply produced.

When the alternating current electrolysis groove of auxiliary electrode that use has an anode current of shunting main pole carries out the processing of electrolysis asperities, such as the spy open clear 60-43500 communique and spy open in the flat 1-52098 communique record, can be diverted to the current value of the anode current on the auxiliary electrode by control, regulate Q _c/ Q _a

With regard to current density, the galvanic anode cycle side I of peak value place of preferred trapezoidal wave _a, cathode deposition period side I _cAll at 10-200A/dm ²I _a/ I _cIn the scope of 0.5-3, be advisable.

Among the present invention, the electrolytic cell that can use with known surface treatments such as perpendicular type, plane, radial patterns with employed electrolytic cell in the electrochemistry asperities processing of alternating current, but preferably especially open radial pattern electrolytic cell or the plane electrolytic cell of putting down in writing in the flat 5-195300 communique with the spy.Electrode is made main electrode, is best with ferrite as impressed current anode with carbon.

In addition, the electrolysis asperities treating apparatus of several alternating current electrolysis groove arranged in series is also applicable.

Electrolytic cell with impressed current anode, can be arranged on before the electrolytic cell of main pole or thereafter, but, has the electrolytic cell of making impressed current anode used in the electrochemistry asperities chemical industry preface of main component with hydrochloric acid, suitable being placed on before the electrolytic cell with main pole, this is desirable especially aspect the mottled generation of attenuating processing.

In addition, if the distance that has the inlet (liquid level) of the electrolytic cell of auxiliary electrode and have between the inlet (liquid level) of the electrolytic cell of main pole is oversize, then in the chemolysis reaction of hydrochloric acid, interphase in the aluminium sheet is dissolving just, form dell, then the image recording layer of this part will be coated with thickly, becomes the mottled of when printing.Therefore, the time of aluminium sheet from the inlet (liquid level) of electrolytic cell to the inlet (liquid level) of electrolytic cell with main pole with auxiliary electrode, with below 3 seconds for well.

In the processing of electrolysis asperities, if in the alternating current electrolysis groove more than 1 or 2, be not set at more than 1 time between the down-time period of indirect current between the main pole of the power supply terminal that binding polarity is different in an electrolytic cell and the aluminium sheet between the main pole and these main poles, and the length between the described down-time period is made as 0.001-0.6 second, then on the whole surface of aluminium sheet, just can be formed uniformly the honeycomb hole, therefore preferred.Be 0.005-0.55 second comparatively ideal idle hours, and better is 0.01-0.5 second.

The time of indirect current is not made as 0.001-20 and is advisable second on the aluminium sheet between an alternating current electrolysis groove and another alternating current electrolysis groove when using the alternating current electrolysis groove more than 2 of arranged in series.Better be 0.1-15 second, best be 1-12 second.

Represented to be applicable to the profile schema diagram of electrolysis asperities treating apparatus one example of the present invention, as to possess plane alternating current electrolysis groove among Fig. 2.Among Fig. 2, the 2nd, alternating current electrolysis groove, 4A, 4B and 4C are respectively main poles, and 6A and 6B are respectively transfer rollers, and 8A is a guide-in roller, and 8B is an outlet roller, the 100th, electrolysis asperities treating apparatus.Electrolysis asperities treating apparatus 100 is that the direction of an edge approximate horizontal carries aluminium sheet W this to be added three-phase alternating current (to call " three-phase alternating current " in the following text), the electrolysis asperities treating apparatus that carries out the processing of electrolysis asperities on one side continuously.

Electrolysis asperities treating apparatus has: along aluminium sheet W direction of transfer a extend and above the alternating current electrolysis groove 2 of unlimited tray shape; Near the bottom surface of alternating current electrolysis groove 2 along direction of transfer a and three tabular

main pole

4A, 4B and 4C be arrangeding in parallel with respect to transmission plane T as the transmission route of aluminium sheet W; Configuration be the inside of alternating current electrolysis groove 2 with respect to the upstream end (following is called " upstream end ") of direction of transfer a and with respect near the end of the downstream part (following is called " downstream part ") of direction of transfer, at alternating current electrolysis groove 2 inner transfer roller 6A and the 6B that transmit aluminium sheet W; Be positioned at alternating current electrolysis groove 2 the top upstream end and aluminium sheet W is directed in the guide-in roller 8A of alternating current electrolysis groove 2 inside; The downstream part that is positioned at the top of alternating current electrolysis groove 2 also will export to the outlet roller 8B of the outside of alternating current electrolysis groove 2 through the aluminium sheet W of alternating current electrolysis groove 2 inside.At the above-mentioned acidic aqueous solution of the inside of alternating current electrolysis groove 2 contain.

Main pole

4A, 4B and 4C respectively with the AC power T that produces three-phase alternating current _AcU terminal, V terminal and W terminal join.Therefore, put on the alternating current on

main pole

4A, 4B and the 4C, each differs from 120 ° its phase place.

Introduce the effect of electrolysis asperities treating apparatus 100 below.

Aluminium sheet W,, is transmitted with certain speed along direction of transfer a again by

transfer roller

6A and 6B through the inside that guide-in roller 8A enters alternating current electrolysis groove 2.

In the inside of alternating current electrolysis groove 2, aluminium sheet W carries out parallel moving for

main pole

4A, 4B and 4C, meanwhile, by

main pole

4A, 4B and 4C it is applied alternating current.So, anode reaction and cathode reaction just alternately take place on aluminium sheet W, when anode reaction takes place, mainly produce the honeycomb hole, when cathode reaction takes place, mainly generate the film of aluminium hydroxide, the surface is by asperitiesization.

Be applied to the alternating current on

main pole

4A, 4B and the 4C, as mentioned above, because 120 ° of its phase phasic differences, so, on main pole 4B, than the slow 120 ° phase place (V phase) of the phase place (U phase) of main pole 4A, anode reaction and cathode reaction take place repeatedly, on main pole 4C, than the slow 120 ° phase place of main pole 4B (W phase), anode reaction and cathode reaction take place repeatedly also.

Therefore, on aluminium sheet W, compare during the electric current of the single-phase alternate mode identical with applying frequency, anode reaction and cathode reaction take place repeatedly with 3 times frequencies, even so when carrying out the processing of electrolysis asperities, also be difficult for producing the chatter mark of travers shape with high speed transmission and high current density.

Represented to be applicable to another routine profile schema diagram that possesses the electrolysis asperities treating apparatus of plane alternating current electrolysis groove of the present invention among Fig. 3.Among Fig. 3, the symbol identical with Fig. 2, described symbol components identical among expression and Fig. 2,10 expression auxiliary electrolytic cells, 12 expression auxiliary electrodes, 14A and 14B represent transfer roller, 16A represents guide-in roller, 16B represents outlet roller, 102 expression electrolysis asperities treating apparatus, and Th1, Th2 and Th3 represent silicon controlled rectifier (SCR).

Electrolysis asperities treating apparatus 102 is devices that the leading portion of the alternating current electrolysis groove 2 that possessed in above-mentioned electrolysis asperities treating apparatus 100 has set the electrolysis asperities processing of auxiliary electrolytic cell 10.

Auxiliary electrolytic cell 10 is box-structures that the top is opened wide, near the bottom surface, with respect to the transmission plane T of the aluminium sheet W tabular auxiliary electrode 12 that be arranged in parallel.

Near the wall of the upstream side of auxiliary electrolytic cell 10 and the wall vicinity in downstream be provided with transfer roller 14A and the 14B that above auxiliary electrode 12, transmits aluminium sheet W.In addition, upstream side above auxiliary electrolytic cell 10 is provided with the guide-in roller 16A that aluminium sheet W is directed in auxiliary electrolytic cell 10 inside, and the downstream above auxiliary electrolytic cell 10 is provided with the aluminium sheet that will pass through auxiliary electrolytic cell 10 inside and exports to outside outlet roller 16B.Above-mentioned acidic aqueous solution in auxiliary electrolytic cell 10 internal storage.

AC power T _AcU phase, V reach W mutually and join with auxiliary electrode 12 respectively mutually, and reach W mutually at U phase, V and installed silicon controlled rectifier (SCR) Th1, Th2 and Th3 respectively additional mutually and between the auxiliary electrode 12.Silicon controlled rectifier (SCR) Th1, Th2 and Th3 can make electric current from AC power T when all connecting into build-up of luminance (scratch start) _AcFlow to auxiliary electrode 12.Therefore, no matter among build-up of luminance silicon controlled rectifier (SCR) Th1, Th2, the Th3 which, all can flow through anode current on the auxiliary electrode 12, so, by the phase place of control silicon controlled rectifier (SCR) Th1, Th2, Th3, can control the current value of the anode current that flows on the auxiliary electrode 12, therefore also can control Q _c/ Q _aValue.

Represented the profile schema diagram of suitable electrolysis asperities treating apparatus one example that has radial pattern alternating current electrolysis groove among the present invention among Fig. 4.Among Fig. 4,20 expression alternating current electrolysis grooves, 26A and 26B represent main pole respectively, 34 expression auxiliary electrolytic cells, 35 expression upstream side deflector rolls, 36 expression auxiliary electrodes, 22 expression alternating current electrolysis groove bodies, 22A represents opening portion, 24 expression transfer rollers, 28A and 28B represent the feed flow nozzle respectively, and 30A represents the upstream side deflector roll, and 30B represents the downstream deflector roll, 32 expression overflow launders, 34A represents the bottom surface of auxiliary electrolytic cell, 104 expression electrolysis asperities treating apparatus, and Th4 and Th5 represent silicon controlled rectifier (SCR) respectively.

Electrolysis asperities treating apparatus 104 has: the alternating current electrolysis groove 20 that possesses the alternating current electrolysis groove body 22 of storing acidic aqueous solution; With to be placed in alternating current electrolysis groove body 22 inner and rotatably be provided in around the axis that along continuous straight runs extends and the left side of aluminium sheet from Fig. 4 the transfer roller 24 that direction of transfer a transmits in the edge to the right.Above-mentioned acidic aqueous solution in the internal storage of alternating current electrolysis groove body 22.

The internal face of alternating current electrolysis groove body 22 forms roughly cylindric, to surround transfer roller 24, clips

main pole

26A and 26B that transfer roller 24 is provided with the semicircle tubular on described internal face.

Main pole

26A and 26B are divided into a plurality of small electrodes, and the dividing plate of insulating properties is housed between small electrode.Small electrode can be with forming as graphite or metal, and dividing plate can be with forming as vinyl chloride resin.The thickness of dividing plate is advisable with 1-10mm.In addition, represented simply among Fig. 4 small electrode among main pole 26A and the 26B, that cut apart by dividing plate separately all with AC power T _AcBe connected.

On the top of alternating current electrolysis groove 20, aluminium sheet W is directed in the alternating current electrolysis groove body 22, in addition, also be formed with the peristome 22A that is used to derive aluminium sheet.Near the peristome 22A of alternating current electrolysis groove body 22, be provided with the feed flow nozzle 28A that replenishes acidic aqueous solutions to alternating current electrolysis groove body 22.In addition, also established feed flow nozzle 28A in addition.

Near peristome 22A above the alternating current electrolysis groove 20, be provided with aluminium sheet W is directed in one group of upstream side deflector roll 30A of alternating current electrolysis groove body 22 inside and will exports to one group of outside downstream deflector roll 30B through the aluminium sheet W of electrolysis asperities processing in alternating current electrolysis groove body 22.

In alternating current electrolysis groove 20, be provided with the overflow launder 32 adjacent with the downstream of alternating current electrolysis groove body 22.Overflow launder 32 internal storage above-mentioned acidic aqueous solution.Overflow launder 32 can temporarily be stored the acidic aqueous solution that overflows from alternating current electrolysis groove body 22, have the liquid level that makes the acidic aqueous solution in the alternating current electrolysis groove body 22 and keep constant function.

Leading portion (upstream) at alternating current electrolysis groove body 22 is provided with auxiliary electrolytic cell 34.Auxiliary electrolytic cell 34 is also more shallow than alternating current electrolysis groove body 22, and bottom surface 34A forms plane.And, on the 34A of bottom surface, be provided with many columned auxiliary electrodes 36.Storing above-mentioned acidic aqueous solution in the auxiliary electrolytic cell 34.

Auxiliary electrode 36 forms suitable by the contour corrosion-resistant metal of platinum, the plain body of ancient unit of weight, equal to 1/24 liang etc.In addition, auxiliary electrode 36 also can be tabular.

Auxiliary electrode 36 is connected with the side of main pole 26A in AC power Tac, 26A is connected in parallel with main pole, during the silicon controlled rectifier (SCR) Th4 that ins succession so that during build-up of luminance, electric current is from AC power T _AcIn a described effluent to auxiliary electrode 36.

In addition, at AC power T _AcIn be connected with main pole 26B a side also link to each other with auxiliary electrode 36 by silicon controlled rectifier (SCR) Th5.When also connecting into build-up of luminance, silicon controlled rectifier (SCR) Th5 can make electric current from AC power T _AcIn be connected with main pole 26B a side direction auxiliary electrode 36 flow.

Among build-up of luminance silicon controlled rectifier (SCR) Th4 and the Th5 which no matter, anode current all can flow on the auxiliary electrode 36.Therefore, by the phase place of control silicon controlled rectifier (SCR) Th4 and Th5, just can control the current value of the anode current that flows through on the auxiliary electrode 36, thereby also can control Q _c/ Q _aValue.

Introduce the effect of electrolysis asperities treating apparatus 104 below

Aluminium sheet W is from the left of Fig. 4, and at first in upstream side deflector roll 35 was directed to auxiliary electrolytic cell 34, then, 30A was directed in the alternating current electrolysis groove body 22 by the upstream side deflector roll.Afterwards, through transfer roller 24 from the left of Fig. 4 to right-hand transmission, export to the outside through downstream deflector roll 30B again.

In alternating current electrolysis groove body 22 and auxiliary electrolytic cell 34 inside, by putting on the alternating current and the effect that puts on the anode current on the auxiliary electrode 36 on main pole 26A and the 26B, among the aluminium sheet W towards the surface of

main pole

26A and 26B side by asperitiesization, can form almost honeycomb hole uniformly.

(4) recirculation of used waste liquid in the asperities processing

Used liquid (waste liquid) in each asperities processing, recirculation as much as possible use to well.

In being dissolved with the aluminum ions caustic soda aqueous solution, aluminium can be separated with caustic soda by crystallisation.In being dissolved with aluminum ions aqueous sulfuric acid, aqueous solution of nitric acid or aqueous hydrochloric acid solution, by the effect of electroosmose process and ion exchange resin, recyclable sulfuric acid or nitric acid.

In being dissolved with aluminum ions aqueous hydrochloric acid solution, opening the evaporation of putting down in writing in the 2000-282272 communique by the spy and also can reclaim.

Among the present invention, preferably the waste liquid with the electrolyte used in the processing of electrochemistry asperities is used for the decontamination treatment process.

In addition, the decontamination carried out before processing of electrochemistry asperities or anodized is handled, and the preferred solution that uses the kind identical with asperities processing of carrying out after decontamination is handled or anodized uses the solution of same composition then better.Thus, can save the washing step that is provided with between decontamination processing and the next process, equipment is simplified and reduce waste liquid amount.

((alkaline etching is handled for the second time) handled in the chemical etching in the aqueous alkali)

After the processing of electrochemistry asperities, carry out second time alkaline etching and be treated to.Handle through current, can make the lithographic plate of even, anti-seal of surface of aluminum plate shape and printing performance excellence.

For the second time to handle be etched by above-mentioned aluminium sheet being contacted with aqueous slkali carry out to alkaline etching.The kind of alkali, be identical during with the alkaline etching processing with the method for aluminium sheet and aqueous slkali contact and used device.

Also can enumerate material identical when handling as alkali used in the aqueous slkali with alkaline etching.

Though the concentration of aqueous slkali can decide according to etch quantity,, % is advisable with the 0.01-80 quality.The temperature of aqueous slkali is advisable with 20-90 ℃.Processing time is advisable with 1-60 second.

In the second time, alkaline etching was handled, the meltage of aluminium sheet (having carried out the surface of electrolysis asperities processing), that desirable is 0.001-30g/m ², that better is 0.1-10g/m ², optimal is 0.2-5g/m ²

((decontamination is for the second time handled) handled in the decontamination in the acidic aqueous solution)

After alkaline etching is handled for the second time, carry out the decontamination second time and be treated to suitable.

Decontamination for the second time handle be by as to make above-mentioned aluminium sheet and concentration be that the method that the acid solutions (aluminium ion that contains 0.01-5 quality %) such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid of 0.5-30 quality % contact is carried out.The method that makes the contact of aluminium sheet and acid solution is identical during with the 1st decontamination processing.

Handle and during decontamination for the third time handles in second time decontamination, as acid solution, with the waste liquid of the sulfuric acid solution of discharging in the anodized described later for well.In addition, replacing the also available sulfuric acid concentration of this waste liquid is that 100-600g/L, aluminium ion concentration are that 1-10g/L, liquid temperature are 30-90 ℃ sulfuric acid solution.

The liquid temperature that decontamination is for the second time handled is advisable with 25-90 ℃.In addition, the processing time of handling of decontamination for the second time with 1-180 second for well.In handling, second time decontamination also can dissolve in aluminium and al alloy component in the used acid solution.

(anodized)

In order to improve the wearability of surface of aluminum plate, can carry out anodized.As the electrolyte of using in the aluminium sheet anodized,, all can use so long as can form the material of porous matter oxide-film.General sulfuric acid, phosphoric acid, oxalic acid, chromic acid or their mixed liquor of using.

These electrolytical concentration can suitably be determined according to electrolytical kind.

Anodised treatment conditions, because of used electrolytical difference changes, so cannot treat different things as the same, still, in general, electrolytical concentration is 1-80 quality %, 5-70 ℃ of liquid temperature, current density 1-60A/dm ², voltage 1-100V, electrolysis time just can in 10 seconds-300 seconds scope.Sulfuric acid process is handled with DC current usually, still, also can use alternating current.The amount of anode oxide film is at 1-5g/m ²Scope in be advisable.If compare 1g/m ²Also few, then anti-seal non-image part undesirable or lithographic plate easily is scratched, and simultaneously, scratches part and can adhere to printing ink, promptly easily produces the so-called dirt that scratches.In addition, if the amount of anode oxide film increases, then since oxide-film easily in the etched segment set of aluminium sheet, so the difference of etched part of aluminium sheet and core oxide-film amount is at 1g/m ²Below for well.

About the anodic oxidation in the aqueous sulfuric acid, open clear 54-128453 communique and spy the spy and open in the clear 48-45303 communique and be documented.Sulfuric acid concentration 10-300g/L, aluminium ion concentration 1-25g/L in the aqueous sulfuric acid of 50-200g/L, add aluminum sulfate for well, and it is best making aluminium ion concentration reach 2-10g/L.The liquid temperature with 30-60 ℃ for well.During with direct current method, current density is 1-60A/dm ², with 5-40A/dm ²For best.When aluminium sheet is carried out anodic oxidation continuously, initial for concentrating of the electric current that prevents to be referred to as to call the aluminium sheet burning, preferably at 5-10A/dm ²Low current density under carry out anodized, enter the second half section after, current density is slowly brought up to 30-50A/dm ², or higher.Current density slowly rises to suitable with the step form in 5-15.In each section, has independently supply unit, with the current value control current density of this supply unit.Method of supplying power to without conductor roller liquid power supply mode for well.The spy opens and has enumerated one of them example in the 2001-11698 communique.

In aqueous sulfuric acid, can be dissolved with the micro constitutent element that contains in a spot of aluminium sheet.In the aqueous sulfuric acid in anodized, owing to can separate out aluminium, so, be necessary to control the concentration and the aluminum ions concentration of sulfuric acid in order to carry out process management.If set aluminum ions concentration low, then must upgrade very continually and carry out anodised aqueous sulfuric acid, waste liquid amount increases, and not only economically, and also can throw into question aspect environment.On the other hand, if set aluminium ion concentration high, then decomposition voltage will uprise, and the cost that increases electric power is uneconomical.Desirable anodised sulfuric acid concentration, aluminium ion concentration, liquid temperature are:

(one)

Sulfuric acid concentration 100-200g/L (130-180g/L more preferably)

Aluminium ion concentration 2-10g/L (3-7g/L more preferably)

30-50 ℃ of liquid temperature (more preferably 33-45 ℃)

(its two)

Sulfuric acid concentration 50-125g/L (80-120g/L more preferably)

Aluminium ion concentration 2-10g/L (3-7g/L more preferably)

40-70 ℃ of liquid temperature (more preferably 50-60 ℃)

In anodized, to the useful conductor roller of mode of aluminium sheet power supply directly to the direct feeding system of aluminium sheet power supply with by the liquid power supply mode of electrolyte to the aluminium sheet power supply.

How direct feeding system is on the anodic oxidation device of following comparison low speed of 30m/min and low current density with on-line velocity, indirectly on the many anodic oxidation devices that surpass the high speed of 30m/min and high current density with on-line velocity of power supply mode.

Indirect power supply mode, as 289 pages in the continuous surface treatment technology (the clear and distribution on September 30th, 61 in complex art center) the above, can adopt the designs of the type of crossing over a hill or linear groove.When high speed and high current density, owing between conductor roller and aluminium sheet, can produce electric spark, so the roller mode of directly powering should not adopt.

No matter be direct feeding system or indirect power supply mode, in order to reduce the energy loss that decline caused because of voltage in the aluminium sheet, especially preferably the anodized operation is divided into two with top, and between the power supply groove of each electrolysis unit and oxidation trough or conductor roller and oxidation trough, connects direct power supply and use.

When adopting direct feeding system, the conductor roller generally is to use aluminium matter.In order to prolong the life-span of roller, such as the spy open in the clear 61-50138 communique record, carry out high temperature homogenization after especially preferably casting and handle with industrial pure, be that crystal is as Al with Al-Fe ₃The raising of the simple layer of Fe corrosion proof aluminium roller.

In the anodized operation, owing to flow through big electric current, so by the effect by the magnetic field that is produced of the electric current that flows through on the bus, Lorentz force can work on aluminium sheet.Its result is owing to plate can be distorted, so the special method of putting down in writing in the clear 57-51290 communique of opening of preferred especially employing.

In addition, because big electric current flows through aluminium sheet, so, by the effect in the magnetic field that produces by the electric current that flows through aluminium sheet, the Lorentz force at the sensing center that transversely can produce of aluminium sheet.Its result, the aluminium sheet frangibility, so, in the anodized groove, be spacing with 100-3000mm, the delivery roll that a plurality of diameters are 100-200mm is set, and make its overlap joint with the angle of 1-15 degree, the phenomenon that is fractureed with the aluminium sheet that prevents to cause by Lorentz force.

Also have, anode oxide film is different at the transversely growing amount of aluminium sheet, and growing amount approaches the amount by the etching generation, and thickness is very thick.Its result, rolling aluminium sheet well just on wrap-up.For this reason, can adopt the method for putting down in writing in special public clear 62-30275 communique or the special public clear 55-21840 communique, solve this problem by stirring liquid stream.In the time can't dealing with problems fully, can and use the aluminium sheet wrap-up with cycle of 0.1-10Hz, with amplitude transversely the swinging of 5-50mm at aluminium sheet to carry out the method for rolling with this method.

In sulfuric acid process, handle with direct current usually, but also can use alternating current.The amount of anode oxide film is adapted at 1-10g/m ²Scope.In general, the anode oxide film amount of planographic printing plate material is 1-5g/m ²If compare 1g/m ²Also few, then anti-seal is good inadequately, and the non-image part of lithographic plate easily is scratched, and simultaneously, scratches part and easily adheres to printing ink, promptly easily produces the so-called dirt that scratches.In addition, if the anode oxide film amount is many, then oxide-film is easily in the etched segment set of aluminium sheet, so the oxide-film amount of the etching part of aluminium sheet and core poor is with 1g/m ²Below be advisable.In the continuous anodized, generally adopt the mode of liquid power supply.As the anode that is used for switching on aluminium sheet, available lead, yttrium oxide, platinum, ferrite etc. still, preferably are the material of main component in order to yttrium oxide.Yttrium oxide covers on the base material through heat treatment.Can use so-called valve-use metals (valvemetal) such as titanium, tantalum, niobium, zirconium as base material, still, be best with titanium or niobium.Because described valve metal resistance ratio is bigger, so, as core copper, wrap the valve metal covering on every side for well at it.When on the copper core, wrapping the valve metal covering, because can not make too complicated shape, so, generally to after being divided into the electrode part capping oxidation iridium that each several part makes, be assembled into required structure with screw bolt and nut etc.

Among the present invention,, preferably the acid waste liquid that produces in the anodized is used for decontamination and handles (the the 1st, the 2nd and the 3rd decontamination processing) from liquor charging equipment, the concentration adjustment device simpleization of decontamination treatment fluid and the angle that reduces equipment cost are considered.

(hydrophilicity-imparting treatment)

Can adopt the known method of hydrophilizing of using always in the manufacturing of support body for lithographic plate printing plate as hydrophilicity-imparting treatment, still, to be treated to alkali silicate.Be elaborated below.

Support through anodized, after handling through washing, with suppress the dissolving of anode oxide film in developer solution, suppress the image recording layer component film forming, improve the anodic oxidation film strength, the adaptation etc. that improves hydrophily, raising and the image recording layer of anode oxide film is purpose, can carry out following processing.One can be enumerated anode oxide film is contacted the silicate processing of handling with alkali-metal aqueous silicate solution.At this moment, the concentration of alkali silicate is 0.1-30 quality %, and that desirable is 0.5-15 quality %, and that better is 0.8-3.0 quality %.5-80 ℃, desirable be 10-70 ℃, better for 15-50 ℃ under, making itself and pH under 25 ℃ is that the aqueous solution of 10-13.5 contacts 0.5-120 second.Make the method for its contact, can be with dipping or by any methods such as sprayer injections.If the pH of alkali metal silicate aqueous solution is lower than 10, liquid will gelation, if than 13.5 height, anode oxide film sometimes will be dissolved.

Can use sodium metasilicate, potassium silicate, lithium metasilicate etc. as alkali silicate used among the present invention.The hydroxide of use has NaOH, potassium hydroxide, lithium hydroxide etc. during the pH value of regulating alkali metal silicate aqueous solution.In above-mentioned treatment fluid, also can cooperate alkali earth metal salt or IVA family (4 family) slaine.Nitrate such as calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate can have been enumerated as alkali salt; Water soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalates, borate.As IVA family (4 family) slaine, can enumerate titanium tetrachloride, titanium trichloride, titanium potassium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetra iodide, basic zirconium chloride etc.Alkaline-earth metal or IVA family (4 family) slaine can use separately also and can matched combined use more than 2 kinds.The desirable consumption of these slaines is 0.01-10 quality %, and that better is 0.05-5.0 quality %.

(sealing is handled)

In addition, also can enumerate the method that various sealings are handled, can adopt as the known water vapour sealing of the sealing processing method of anode oxide film, boiling water (hot water) sealing, slaine sealing (chromate/bichromate sealing, nickel acetate sealing etc.), the sealing of grease dipping, synthetic resin sealing, low temperature sealing (by potassium ferricyanide or alkali earths salt etc.), but consider with aspects such as the performance (with the adaptation and the hydrophily of image recording layer) of support, high speed processing, low cost, low Hazardouses from galley, adopt the water vapour sealing relatively good.As its method can enumerate Ru Te open the record of flat 4-176690 communique, will pressurize or the water vapour of normal pressure in relative humidity is more than 70%, vapor (steam) temperature is under the condition more than 95 ℃, continuously or the discontinuous method of 2-180 about second etc. that contact with anode oxide film.As other sealing processing method, can adopt with support impregnation about 80-100 ℃ hot water or aqueous alkali in or adopt the processing method of spraying, perhaps replace or continue again method with nitrous acid solution dipping or spraying processing.Example as nitrite contained in the nitrous acid solution etc. can be enumerated as LiNO ₂, NaNO ₂, KNO ₂, Mg (NO ₂) ₂, Ca (NO ₂) ₂, Zn (NO ₃) ₂, Al (NO ₂) ₃, Zr (NO ₂) ₄, Sn (NO ₂) ₃, Cr (NO ₂) ₃, Co (NO ₂) ₂, Mn (NO ₂) ₂, Ni (NO ₂) ₂Deng, be preferably alkali nitrates especially.Also can and use the nitrite more than 2 kinds etc.

Treatment conditions are different because of the state and the alkali-metal kind of support, must not make sweeping generalizations, when for example using natrium nitrosum, concentration is generally 0.001-10 quality %, preferably uses 0.01-2 quality %, bathes temperature and is generally from room temperature to about about 100 ℃, be preferably 60-90 ℃, processing time is generally 15-300 second, is preferably 10-180 second, can select from above-mentioned scope respectively during processing.The pH of nitrous acid aqueous solution can be adjusted to 8.0-11.0, preferably is adjusted to 8.5-9.5.When being adjusted to the pH of nitrous acid aqueous solution in the above-mentioned scope, using and be advisable as alkaline buffer solution.Though as this alkaline buffer solution without limits, should use the mixed aqueous solution etc. of mixed aqueous solution, sodium tetraborate and NaOH of mixed aqueous solution, hydrochloric acid and sodium carbonate of mixed aqueous solution, sodium chloride and NaOH of mixed aqueous solution, sodium carbonate and sodium acid carbonate of mixed aqueous solution, sodium carbonate and the NaOH of sodium acid carbonate and NaOH.In addition, above-mentioned alkaline buffer solution, the alkali metal salt except sodium, also available as sylvite etc.After having carried out above-mentioned silicate processing and sealing processing, in order to improve the adaptation with image recording layer, can carry out the spy and open acidic aqueous solution processing or the hydrophily bottoming of putting down in writing in the flat 5-278362 communique, the spy also can be set open flat 4-282637 communique or the special organic layer of putting down in writing in the flat 7-314937 communique of opening.

In the preparation of support body for lithographic plate printing plate of the present invention, except carrying out above-mentioned processing, also can carry out following processing.

(method for washing of aluminium sheet)

Aluminium sheet is handled in acid or aqueous alkali, perhaps carry out mechanical asperities processing with grinding agent after, for remove soup and grinding agent from surface of aluminum plate, washing procedure is set usually.

The washing procedure operated by rotary motion is between the different treatment trough of kind, the composition of soup, and the time that enters the time of washing procedure or the treatment trough below washing procedure enters from treatment trough was generally below 10 seconds, was preferably 0.1-10 second.If surpass 10 seconds, chemical modification can be carried out in the surface, and easily generation is handled mottled sometimes.

Treatment trough before and after the washing step and the interval between the treatment trough, the time of passing through with aluminium sheet below 15 seconds for well, being best below 5 seconds.If surpass 15 seconds, on the surface chemical modification can take place then, cause being difficult in the following operation carry out uniform asperities processing sometimes.

During the washing aluminium sheet, adopting following method for well, is purpose to reduce displacement, and it is good adopting the water-washing method of dry ice powder.

(1) water washs

As the washing methods of support body for lithographic plate printing plate, commonly used is to utilize the water washing that sprays from spary tip to be squeezed out the method on the surface of liquid by roll.Water sprays with the angle of 45-90 degree towards the downstream of aluminium sheet moving direction is advisable.The expulsion pressure of water, the pressure gauge just to have ejected from jet blower is generally 0.5-5kg/cm ², the liquid temperature with 10-80 ℃ for well.The translational speed of the aluminium sheet that moves is advisable with 20-200m/min.The water yield of spraying on the aluminium sheet is in a washing procedure, with 0.1-10L/m ²Liquid measure spray and to be advisable.In a sink, minimum minimum by 2 above jet pipe jet cleaning water on the surface of aluminium sheet by 2 above jet pipes, its back side.Interval with 50-200mm on a jet pipe is provided with 5-30 spary tip.The spray angle of spary tip is to be advisable with 10-250mm in the interval of the jet face of 10-150 degree, aluminium sheet and spary tip.The section shape of the spraying of spary tip (spray pattern) has ring-type, circle, ellipse, square, rectangle etc., but be advisable with circle or ellipse or square or rectangular.Flow distribution (spraying the distribution state of the water yield on the surface of aluminum plate) has annular distribution, evenly distribution, mountain type distribution etc., but, use when on the injection spray pipe sprayer of several spary tips being arranged side by side, be distributed as with the mountain type that on whole plate face, forms the uniform flux distribution easily.Flow distribution changes with the distance of atomisation pressure and spary tip and aluminium sheet.The particle diameter of spraying changes with structure, atomisation pressure, the spray amount of spary tip, but with 10-10000 μ m for well, be best with 100-1000.The material of nozzle is to have wearability for well to swiftly flowing liquid.Its material can be used brass, stainless steel, pottery etc., but is best to use ceramic nozzle.

The direction of advance that is provided with the relative aluminium sheet of nozzle of spary tip can be with the angle configurations of 45-90 degree, and still, center line and aluminium sheet direction of advance on the long direction of spray pattern Center Length meet at right angles to good.

Through the wash time of washing treatment process, industrial with below 10 seconds for well, with 0.5-5 second be best.

(2) washing of using the dry ice powder to carry out

In the method for the washing that the two sides of aluminium sheet injection dry ice powder carries out, can use the spy to open the known abrasive jet cleaning device of putting down in writing in the flat 10-66905 communique.What jet blower was used is that the spy opens flat 10-28901 communique, the spy opens the known jet blower of putting down in writing in the flat 10-28902 communique, several this nozzle arrangement can be used on the aluminium sheet two sides.Jet blower can transverse row in line, still, for the spray pattern that makes surface of aluminum plate overlapping to some extent on the width of aluminium sheet, so jet blower is obliquely installed to good.The interval of jet blower and aluminium sheet for well, is best with 10-50mm with 1-100mm.

In addition, in the method for the Powdered dry ice of preparation, can use the real manufacturing installation of putting down in writing in the flat 7-38104 communique of opening.Spray the gas of usefulness and can use GN ₂Gas, available air also.The particle diameter of Powdered dry ice is 1-1000 μ m, and its average grain diameter is advisable with 10-100 μ m.The LCO of a jet blower ₂The quantity delivered of (liquefaction carbonic acid gas) with 0.1-1kg/min for well, its supply pressure with 1-20MPa for well.Washing pressure on the aluminium sheet is advisable with 1-20MPa.

(material of delivery roll (パスロ one Le))

Roller can be used the roller of selecting in the metallic roll used from the surface, resin roll, rubber rollers, the nonwoven cloth rewinder roll through the tinuous production of plating is handled or lining (lining) is handled known iron and steel, plating, electrolytic capacitor, original edition of lithographic printing plate etc.

The physics value on the material of roller, surface can be according to the soup and the state on aluminium surface at that time, and considers that corrosion resistance, wearability, hear resistance, drug resistance wait selected.If use metallic roll, generally use chromed hardened roller.In the rubber rollers, natural rubber, isoprene rubber, styrene butadiene ribber, butadiene rubber, butyl rubber, chloroprene rubber, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, acrylic rubber, ECD, polyurethane rubber, polysulfide rubber, fluorubber etc. can be used, also the material that in them, has added trace assistant can be used certainly.The international rubber hardness degree standard of rubber rollers (stipulating among the JIS K6253) is best with 60-90.

Preparation method according to the support body for lithographic plate printing plate of above-mentioned detailed description, even under the situation that adopts low-purity aluminium sheet (contain the aluminium sheet of many alloy compositions or do not regulate the aluminium sheet of alloying component), also can obtain the uniform support body for lithographic plate printing plate of concave-convex surface.In addition, by the support body for lithographic plate printing plate that the preparation method of above-mentioned support body for lithographic plate printing plate makes, as described later,, makes image recording layer original edition of lithographic printing plate of the present invention if being set, when then lithographic plate is made in its plate-making, its printing performance excellence and anti-seal are good.

[original edition of lithographic printing plate]

Original edition of lithographic printing plate of the present invention is provided with the image recording layer that can form image by heat and obtains on above-mentioned support body for lithographic plate printing plate.

(priming coat)

Among the present invention, before on the support body for lithographic plate printing plate that so makes image recording layer being set, as required, also can be provided with as inorganic bottom coating or organic priming coat with water-soluble metal salts such as Firebrake ZBs.

Can enumerate as carboxymethyl cellulose as the organic compound of using in organic priming coat; Dextrin; Gum arabic; Polymer and copolymer that sulfo group is arranged on the side chain; Polyacrylic acid; 2-amino-ethyl phosphonic acids etc. has amino phosphonic acid based; Can have organic phospho acids such as substituent phenyl-phosphonic acid, naphthyl phosphonic acids, alkyl phosphonic acid, glycerine phosphonic acids, methylene di 2 ethylhexyl phosphonic acid, ethylene di 2 ethylhexyl phosphonic acid; Can have organic phosphoric acids such as substituent phosphenylic acid, naphthyl phosphoric acid, alkyl phosphoric acid, phosphoglycerol; Can have organic phosphinic acids such as substituent phenyl phosphinic acid, naphthyl phosphinic acids, alkyl phosphinic acid, glycerine phosphinic acids; Amino acids such as glycine, Beta-alanine; The hydrochloride of triethanolamine etc. has the hydrochloride of the amine of hydroxyl; Weld.Wherein, the preferred macromolecular compound with the constituent that contains acidic group that uses especially preferably has the macromolecular compound that contains the acidic group constituent and contain the constituent of alkali simultaneously.They can use separately, also can use mixing more than 2 kinds.

(macromolecular compound) with the constituent that contains acidic group

As acidic group used in the macromolecular compound with the constituent that contains acidic group, with acid dissociation constant (pKa) be acidic group below 7 for well, be more preferably-COOH ,-SO ₃H ,-OSO ₃H ,-PO ₃H ₂,-OPO ₃H ₂,-CONHSO ₂,-SO ₂NHSO ₂-, best be-COOH.The constituent that contains acidic group both can use separately, also can be used in combination more than 2 kinds.

Above-mentioned macromolecular compound is acrylic resin or vinyl class in polymer such as methacrylic resin or polystyrene with the backbone structure, polyurethane resin, and the polymer of polyester or polyamide is for well.Wherein, backbone structure is that vinyl class in polymer such as acrylic resin or methacrylic resin or polystyrene are for preferred.

In addition, when above-mentioned macromolecular compound has the constituent that contains alkali, it is desirable to contain the alkali of the atom of periodic table 15 families (VB family) or 16 families (group vib) as alkali, better is the alkali that contains nitrogen-atoms, phosphorus atoms or sulphur atom, it would be desirable the alkali of nitrogen atom.

It is above for well that above-mentioned macromolecular compound contains above-mentioned 1 mole of % of constituent that contains alkali, contain 5 moles then better more than the %.If contain 1 mole of the above-mentioned constituent that contains alkali more than the %, then adaptation can further improve.

In addition, the above-mentioned macromolecular compound with the constituent that contains alkali with 20 moles of the constituents that contain acidic group more than the % for well, serve as better more than the % to contain 40 moles.If the above-mentioned constituent that contains acidic group is contained 20 moles more than the %, can further promote dissolving to remove when then alkali develops, and because the cooperative effect of acidic group and alkali, adaptation also can further improve.Have, the constituent that contains alkali both can use separately again, also can will be used in combination more than 2 kinds.

Form the used above-mentioned macromolecular compound of priming coat, also can the compound more than 2 kinds that constituent, ratio of components or molecular weight is different use.

The typical example of macromolecular compound that has the constituent that contains acidic group simultaneously and contain the constituent of alkali is listed below.The ratio of components of polymer architecture is represented mole percent.

[changing 1]

The typical case of macromolecular compound

Structural molecule amount (Mw)

[changing 2]

The typical case of macromolecular compound

Structural molecule amount (Mw)

[changing 3]

The typical case of macromolecular compound

Structural molecule amount (Mw)

[changing 4]

The typical case of macromolecular compound

Structural molecule amount (Mw)

2.5 ten thousand

3.3 ten thousand

4.1 ten thousand

1.4 ten thousand

[changing 5]

The typical case of macromolecular compound

Structural molecule amount (Mw)

2.2 ten thousand

2.3 ten thousand

4.7 ten thousand

3.5 ten thousand

Form the general available free radical chain polymerization method preparation of the used above-mentioned macromolecular compound of priming coat (with reference to " Text book of polymer Science " 3rd ed. (1984) F.W.Billmeyer, AWiley-InterScience Publication).

The molecular weight ranges of above-mentioned macromolecular compound can be than broad, and still, when using light scattering determining, weight average molecular weight (Mw) for well, is better with 1000-600000 with 500-2000000.In addition, the scope of the amount of contained unreacted monomer can broad in this macromolecular compound, but to contain below the 20 quality % for well, serves as better to contain below the 10 quality %.

(forming the method for making of the used macromolecular compound of priming coat etc.)

Below, with above-named be example to vinyl benzoic acid and the muriatic copolymer of vinyl benzyl trimethylammonium (above-mentioned No.1), expression has the constituent that contains acidic group simultaneously and contains the synthesis example of macromolecular compound of the constituent of alkali, and other macromolecular compound also can use the same method synthetic.

In the 1L there-necked flask, 146.9g (0.99mol) pack into to vinyl benzoic acid (industrial society system is learned in northern Xinghua), 44.2g (0.21mol) vinyl benzyl trimethylammonium chloride and 446g 2-methyl cellosolve, heating while stirring remains on 75 ℃ under stream of nitrogen gas.Add 2.76g (12mmol) 2 in this solution, two (isobutyric acid) dimethyl esters of 2-azo continue to stir.After 2 hours, add 2.76g (12mmol) 2 again, two (isobutyric acid) dimethyl esters of 2-azo continue to stir.Stir after 2 hours, naturally cool to room temperature.This solution under agitation is injected in the ethyl acetate of 12L.The solid of separating out is leached, and make its drying.Its output is 189.5g.To the solid that makes with light scattering determining molecular weight, its result, weight average molecular weight (Mw) is 3.2 ten thousand.

(formation of priming coat)

Priming coat is above-mentioned macromolecular compound to be ined all sorts of ways be coated on above the above-mentioned support body for lithographic plate printing plate and be provided with.

As the method that priming coat is set, can enumerate to be dissolved in the mixed solvent of organic solvents such as methyl alcohol, ethanol, butanone or their mixed solvent or these solvents and water and make solution as: above-mentioned macromolecular compound, again with this solution coat on support body for lithographic plate printing plate, make it dry and the method for priming coat is set; Above-mentioned macromolecular compound is dissolved in the mixed solvent of organic solvents such as methyl alcohol, ethanol, butanone or their mixed solvent or these organic solvents and water and makes solution, support body for lithographic plate printing plate is immersed in the above-mentioned solution again, after making its adsorbed polymer compound, washing such as water also makes it dry and the method for priming coat is set.

In last method, the coating concentration that can in all sorts of ways is the solution of the above-mentioned macromolecular compound of 0.005-10 quality %.As adopting rod to be coated with any method in machine coating, rotation coating, spraying, the coating of curtain formula etc.In addition, in one method of back, the concentration of solution is 0.01-20 quality %, and that desirable is 0.05%-5 quality %.Dipping temperature is 20 ℃-90 ℃, and desirable is 25-50 ℃, and dip time is 0.1 second-20 minutes, and desirable is 2 seconds-1 minute.

Above-mentioned solution can be used alkaline matters such as ammonia, triethylamine, potassium hydroxide; Inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid; Organic sulfonic acid such as nitrobenzene-sulfonic acid, naphthalene sulfonic acids; Organic phospho acids such as phenyl-phosphonic acid; Various organic acidity materials such as organic carboxyl acid such as benzoic acid, coumaric acid, malic acid; Organic acyl chlorides such as naphthalene sulfonyl chloride, benzene sulfonyl chloride etc. are regulated the pH value, and pH is 0-12, are preferably in the pH0-5 scope to use.

The dried coating weight of macromolecular compound that forms priming coat is with 2-100mg/m ²Be advisable, be preferably 5-50mg/m ²If above-mentioned coating weight compares 2mg/m ²Few, then can not get effect of sufficient sometimes.In addition, if compare 100mg/m ²Many, then the result is same.

(image recording layer)

As the image recording layer that can form image by the effect of heat, can enumerate as temperature-sensitive eurymeric, hot minus and exempt from the processing type.Below, just the temperature-sensitive eurymeric image recording layer that is suitable for describes.

The image recording layer of temperature-sensitive eurymeric contains (A) water-insoluble and the resin (to call " alkali soluble resins " in the following text) of alkali-soluble and (B) infrared absorbent.

(A) alkali soluble resins

Spendable in the image recording layer of temperature-sensitive eurymeric (A) alkali soluble resins comprises the homopolymers, copolymer or their mixture that contain acidic-group on main chain in the macromolecule and/or the side chain.About acidic-group, the method for can adopt the method that makes monomer carry out polymerization in advance and introduce, introducing by the high molecular weight reactive after the polymerization and with the method for they and usefulness with acidic-group, no matter which kind of method can be used.

Do not have special restriction as alkali soluble resins, become the phenolic resins of putting down in writing in the book as using " phenolic resins ", アイピ one シ one (strain) " the synthetic sclerosis Strengthening and Toughening and the application of phenolic resins " at plastics エ one ジ (strain), Nikkan Kogyo Shimbun's " plastic material lecture 15 phenolic resins ", census of manufacturing meeting (strain) " plastics pandect 15 phenolic resins " etc.; Polycarboxylated styrene, poly-halogenated hydroxyl styrene, the copolymer of N-(4-hydroxy phenyl) Methacrylamide, the copolymer of hydroquinone monomethyl acrylate; The sulfimide base polymer of putting down in writing in the Te Kaiping 7-28244 communique; The carboxylic polymer of putting down in writing in the Te Kaiping 7-36184 communique; The spy opens the acrylic resin of putting down in writing in the clear 51-34711 communique that contains the phenol hydroxyl; Various alkali-soluble macromolecular compounds such as the acrylic resin of putting down in writing in the Te Kaiping 2-866 communique, polyurethanes resin with sulfonamido.

Wherein, from considering for the embodiment aspect of the dissolubility of alkaline-based developer and dissolving rejection, the material of acidic groups that contains following (1)-(6) on high molecular main chain and/or side chain is more satisfactory.

(1) the phenol hydroxyl (Ar-OH)

(2) sulfonamido (SO ₂NH-R)

(3) substituted sulphonamide acidic group (SO ₂NHCOR ,-SO ₂NHSO ₂R ,-CONHSO ₂R) (to call " active imido grpup " in the following text)

(4) carboxyl (CO ₂H)

(5) sulfonic group (SO ₃H)

(6) phosphate (OPO ₃H ₂)

Aromatic linked group, R that the middle Ar in above-mentioned (1)-(6) represents to have substituent divalent represent to have substituent alkyl.

In containing the alkali soluble resins that is selected from the acidic groups in above-mentioned (1)-(6), at least the alkali soluble resins that contains a kind of group among (1) phenol hydroxyl, (2) sulfonamido, (3) active imido grpup and (4) carboxylic acid group is for preferred, the alkali soluble resins that particularly contains a kind of group among (1) phenol hydroxyl, (2) sulfonamido and (4) carboxylic acid group at least, even more ideal to the film-strength aspect of dissolubility, development tolerance and the image recording layer of alkaline-based developer.

The alkali soluble resins of the acidic groups of above-mentioned as having (1)-(6), the material that can be listed below.

(1) as having the alkali soluble resins of phenol hydroxyl, can enumerate as: novolac resin, resol, polyvinylphenol resin, contain the acrylic resin of phenol hydroxyl etc.Wherein consider from imaging or Thermocurable angle, preferred novolac resin, resol, polyvinylphenol resin, consider from stable angle, preferred novolac resin, polyvinylphenol resin, consider preferred especially novolac resin from the source of raw material, the angle of versatility.

Novolac resin is meant as phenol, o-cresols, m-cresols, p-cresols, 2, the 5-xylenols, 3, the 5-xylenols, the o-ethyl-phenol, the m-ethyl-phenol, the p-ethyl-phenol, propylphenol, normal-butyl phenol, tert-butyl phenol, the 1-naphthols, beta naphthal, catechol, resorcinol, hydroquinones, pyrogallol, 1,2, the 4-benzenetriol, chloro cresols, 4,4 '-'-biphenyl diphenol, 2, at least a in the phenol such as two (4 '-hydroxy phenyl) propane of 2-, under acidic catalyst, and as formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde, (also available paraformaldehyde replaces formaldehyde to aldehydes such as furfural, replace acetaldehyde with paraidehyde), or and acetone, butanone, at least a in the ketones such as methyl iso-butyl ketone (MIBK) carries out the resin that polycondensation makes.

Among the present invention, preferably as phenol compound phenol, o-cresols, m-cresols, p-cresols, 2,5-xylenols, 3, at least a in 5-xylenols and the resorcinol, and as aldehydes or ketone compounds with at least a condensation polymer in formaldehyde, acetaldehyde and the propionic aldehyde.Preferred especially m-cresols: p-cresols: 2, the 5-xylenols: 3, the 5-xylenols: the mixed proportion of resorcinol is benzene mixed phenolic compound or the phenol of 40-100: 0-50: 0-20: 0-20: 0-20 with the molar ratio computing: m-cresols: the mixed proportion of p-cresols is (mixing) phenol of 0-100: 0-70: 0-60 and the condensation polymer of formaldehyde with the molar ratio computing.

Have again,, can enumerate the polymer of polymerizable monomer with phenol hydroxyl as alkali soluble resins with phenol hydroxyl.

Can enumerate acrylamide, Methacrylamide, acrylate, methacrylate or hydroxy styrenes etc. as polymerizable monomer with phenol hydroxyl with phenol hydroxyl.

Specifically, suitable to N-(2-hydroxy phenyl) acrylamide, N-(3-hydroxy phenyl) acrylamide, N-(4-hydroxy phenyl) acrylamide, N-(2-hydroxy phenyl) Methacrylamide, N-(3-hydroxy phenyl) Methacrylamide, N-(4-hydroxy phenyl) Methacrylamide, o-hydroxy phenyl acrylate, m-hydroxy phenyl acrylate, p-hydroxy phenyl acrylate, o-hydroxy phenyl methacrylate, m-hydroxy phenyl methacrylate, p-hydroxy phenyl methacrylate, the o-hydroxy styrenes, the m-hydroxy styrenes, the p-hydroxy styrenes, 2-(2-hydroxy phenyl) ethyl propylene acid esters, 2-(3-hydroxy phenyl) ethyl propylene acid esters, 2-(4-hydroxy phenyl) ethyl propylene acid esters, 2-(2-hydroxy phenyl) ethyl-methyl acrylate, 2-(3-hydroxy phenyl) ethyl-methyl acrylate, 2-(4-hydroxy phenyl) ethyl-methyl acrylate etc.

In addition, also can be with the polymerization of acidic group presoma to make it importing acidic group again behind the producing high-molecular.For example, also can with the p-acetoxystyrene as the polymerization of acidic group presoma after, again with the ester group partial hydrolysis, import the phenol hydroxyl.

In addition, at United States Patent (USP) the 4th, 123, the tert-butyl benzene fluosite of putting down in writing in No. 279 specifications, octyl phenol formaldehyde resin etc. contain the example that the condensation polymer of the phenol of alkyl that carbon number is 3-8 and formaldehyde also can be done to be fit to as substituting group.

(2), can enumerate as being the polymer that the main composition composition is formed with the minimal structure unit that comes from the compound with sulfonamido as having the alkali soluble resins of sulfonamido.Can be set forth in to contain respectively in the molecule as above-mentioned compound and on the N atom, combine the sulfonamido of a hydrogen atom and the compound of polymerisable unsaturated group more than one at least.Wherein, preferably contain the low molecular compound of the sulfimide base of acryloyl group, pi-allyl or ethyleneoxy (PVC ニロキシ) and mono-substituted amino-sulfonyl or replacement at molecule.Can enumerate as compound with following general formula (I)-(V) expression.

[changing 6]

In the formula, X ¹And X ²Respectively expression-O-or-NR ⁷-.R ¹And R ⁴Represent respectively hydrogen atom or-CH ₃R ², R ⁵, R ⁹, R ¹²And R ¹⁶Expression can contain alkylidene, cycloalkylidene, arlydene or the inferior aralkyl that substituent carbon number is 1-12 respectively.R ⁴, R ⁷And R ¹³Represent hydrogen atom or can contain alkyl, cycloalkyl, the aryl or aralkyl that substituent carbon number is 1-12 respectively.In addition, R ⁶And R ¹⁷Expression can contain alkyl, cycloalkyl, the aryl or aralkyl that substituent carbon number is 1-12 respectively.R ⁸, R ¹⁰And R ¹⁴The expression hydrogen atom or-CH ₃R ¹¹And R ¹⁵Represent that respectively singly-bound maybe can contain alkylidene, cycloalkylidene, arlydene or the inferior aralkyl that substituent carbon number is 1-12.Y ¹And Y ²Represent respectively singly-bound or-CO-.What specifically, can be suitable for has m-aminosulfonyl phenyl methyl acrylate, N-(p-aminosulfonyl phenyl) methacrylate, N-(p-aminosulfonyl phenyl) acrylamide etc.

(3) as alkali soluble resins, can enumerate the polymer of forming as the main composition composition as with the minimal structure unit that comes from the compound with active imido grpup with active imido grpup.As above-mentioned compound, can be set forth in and have the more than one active imido grpup of representing with following structural formula and the compound of polymerisable unsaturated group in the molecule respectively.

[changing 7]

As such compound, specifically can select N-(p-tosyl) Methacrylamide, N-(p-tosyl) acrylamide etc. for use.

(4), can enumerate to come from minimal structure unit in the compound that in molecule, has an above carboxyl and polymerisable unsaturated group respectively as the polymer of main composition composition as having the alkali soluble resins of carboxyl.

(5), can enumerate to come from minimal structure unit in the compound that in molecule, has an above sulfo group and polymerisable unsaturated group respectively as the polymer of main composition composition as alkali soluble resins with sulfo group.

(6), can enumerate to come from minimal structure unit in the compound that in molecule, has an above phosphate and polymerisable unsaturated group respectively as the polymer of main composition composition as having the alkali soluble resins of phosphate.

Minimal structure unit with acidic groups of from above-mentioned (1)-(6), selecting, not necessarily just a kind of, also can use the minimal structure unit that has same acidic groups more than 2 kinds or make the polymer of the minimal structure unit copolymerization that has different acidic groups more than 2 kinds.

In described copolymer, contain 10 moles of compounds that have from above-mentioned (1)-(6) acidic groups of selecting more than the % for well, contain 20 moles of % above for better.This acidic groups is to select from above-mentioned (1)-(6) that make its copolymerization.If 10 moles of % of less than, then alkali solubility is abundant inadequately, can not reach the effect that improves the development tolerance well.

Make the compound copolymerization, when using the alkali soluble resins as copolymer, but also available other compound that does not contain the acidic groups in described (1)-(6) of the compound of copolymerization.As the example that does not contain other compound of acidic groups in (1)-(6), can enumerate the compound of enumerating in following (m1)-(m13), but never be limited to these compounds.

(m1) acrylic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacry-late etc. contain the esters of acrylic acid and the methyl acrylic ester of aliphatic hydroxyl;

(m2) alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, 2-ethyl hexyl acrylate, benzyl acrylate, acrylic acid-2-chloroethene ester, glycidyl acrylate;

(m3) alkyl methacrylates such as methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2-chloroethene ester, GMA;

(m4) acrylamide or Methacrylamides such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-ethyl acrylamide, N-hexyl methyl acrylamide, N-cyclohexyl acrylamide, N-ethoxy acrylamide, N phenyl acrylamide, N-nitrobenzophenone acrylamide, N-ethyl-N phenyl acrylamide;

(m5) vinyl ethers of ethyl vinyl ether, 2-chloroethyl vinyl ethers, ethoxy vinyl ethers, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ethers, Vinyl phenyl ether etc.;

(m6) vinyl esters such as vinylacetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate;

(m7) phenylethylenes such as styrene, AMS, methyl styrene, 1-chloro-4-methyl-benzene, p-acetoxy-styrene;

(m8) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone;

(m9) olefines such as ethene, propylene, isobutene, butadiene, isoprene;

(m10) N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile etc.;

(m11) the maleic anhydride unsaturated imines such as imines, N-acryloyl group acrylamide, N-acetyl group Methacrylamide, N-propiono Methacrylamide, N-(p-chlorobenzene acyl group) Methacrylamide that contract;

(m12) maleic anhydride, furoate clothing acid anhydride, acrylic acid chlorine, methacrylic chloride etc.;

(m13) (for example: the compound of record in the special 2001-115595 of hope specification, the special 2001-115598 of the hope specification etc.) be connected with heteroatomic methacrylic monomer on the α position.

Alkali soluble resins is the polymerizable monomer that described (1) has the phenol hydroxyl among the present invention, (2) has the polymerizable monomer of sulfonamido, (3) has the polymerizable monomer of active imido grpup, when (4) polymerizable monomer (5) with carboxyl has the homopolymers of the polymerizable monomer of sulfo group and the polymerizable monomer that (6) have phosphate or copolymer, its weight average molecular weight is more than 2000, number-average molecular weight be more than 500 for well, preferably weight average molecular weight is 5000-300000, number-average molecular weight is 800-250000, decentralization (weight-average molecular weight/number-average molecular weight) is 1.1-10, and this weight average molecular weight obtains by gel permeation chromatography and through polystyrene conversion.

In addition, when the alkali soluble resins among the present invention was novolac resin, preferable weight-average molecular weight was that 500-100000, number-average molecular weight are 200-50000.Also can use low-molecular-weight component, the particularly few novolac resin of residual monomer components in proportions put down in writing in the special 2001-126278 of the hope specification.

These alkali soluble resins can use a kind of respectively, also can make up more than 2 kinds and use, and the addition in all solids component of image recording layer is 30-99 quality %, and that desirable is 40-95 quality %, and that desirable especially is 50-90 quality %.

If the interpolation insufficient total amount of alkali soluble resins 30 quality %, then the durability of image recording layer is just poor, and is in addition, if surpass 99 quality %, then undesirable sometimes aspect speed and imaging.

When alkali soluble resins is used in collocation, though any combination is all available, but, can enumerate as optimum example: polymer and collocation with polymer of sulfonamido acidic group with phenol hydroxyl, polymer and collocation with phenol hydroxyl with polymer of carboxyl, the collocation that has the polymer of phenol hydroxyl more than 2 kinds, for example: United States Patent (USP) the 4th, the phenol of the alkyl substituent that the tert-butyl phenol of 123, No. 279 specification records and the condensation polymer of formaldehyde or the condensation polymer of octyl phenol and formaldehyde etc. have 3-8 carbon and the condensation polymer of formaldehyde, the spy opens the collocation of alkali soluble resins that contains the phenol structure that has electron-withdrawing group on the aromatic rings of putting down in writing in the 2000-241972 communique etc.

(B) infrared absorbent

Available infrared absorbent among the present invention, so long as can absorb the luminous energy ray and produce hot material, then without limits to its absorbing wavelength scope, but, consider from the height output laser aspect that adapts to easy acquisition, preferably select infrared ray absorbing dyestuff or pigment between the 700-1200nm wavelength for use with absorption maximum.

Can use the known material of putting down in writing in the documents such as commercially available dye well " dyestuff brief guide " (Synthetic Organic Chemistry association compiles, clear and 45 annuals) as dyestuff.Specifically can enumerate: azo dyes, the metal complex azo dyes, the pyrazolin-5-one azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, the naphthalocyanine dyestuff, carboniumion dye, quinoneimine dye, methine dyes, cyanine dyes, Si Kualin (squarylium) pigment, (sulfo-) pyralium salt, metal mercaptide salt complex, indoaniline metal complex class dyestuff, オキソノ one Le dyestuff, the diimonium dyestuff, the amine salt dyestuff, Network ロコニウ system dyestuff, dyestuffs such as intermolecular CT pigment.

As desirable dyestuff, can enumerate and open clear 58-125246 number, spy as: spy and open clear 59-84356 number, spy and open clear 59-202829 number, spy and the cyanine dyes of putting down in writing in each communique such as open clear 60-78787 number; The spy opens clear 58-173696 number, spy and opens clear 58-181690 number, spy and the methine dyes of putting down in writing in each communique such as open clear 58-194595 number; The spy opens clear 58-112793 number, spy and opens clear 58-224793 number, spy and open clear 59-48187 number, spy and open clear 59-73996 number, spy and open clear 60-52940 number, spy and the naphthoquinone dyestuff of putting down in writing in each communique such as open clear 60-63744 number; The spy opens the middle Si Kualin pigments of putting down in writing such as clear 58-112792 communique; The cyanine dyes of putting down in writing in the 434th, No. 875 specification of BP etc.

In addition, the near infrared absorption sensitizer of putting down in writing in the United States Patent (USP) the 5th, 156, No. 938 specifications is also applicable, also has substituted aryl benzo (sulfo-) pyralium salt of putting down in writing in the 3rd, 881, No. 924 communiques of United States Patent (USP); The spy opens three methine thia pyralium salts of record in the clear 57-142645 communique (United States Patent (USP) the 4th, 327, No. 169 specifications); The spy opens clear 58-181051 number, spy and opens clear 58-220143 number, spy and open clear 59-41363 number, spy and open clear 59-84248 number, spy and open clear 59-84249 number, spy and open clear 59-146063 number, spy and open the pyralium salt compounds of putting down in writing in each communique of clear 59-146061 number; The spy opens the cyanines pigment of putting down in writing in the clear 59-216146 communique; The five methine sulfo-pyralium salts of putting down in writing in the United States Patent (USP) the 4th, 283, No. 475 specifications; The pyrylium compound of putting down in writing in special fair 5-13514 communique and the special fair 5-19702 communique also can use.

In addition, as dyestuff, the example of desirable other can be enumerated United States Patent (USP) the 4th, 756, and note is made formula (I) and hear-infrared absorption dye (II) in No. 993 specifications.

The desirable especially cyanines enumerated pigment, phthalocyanine dye, オキソノ one Le dyestuff, Si Kualin pigment, pyralium salt, sulfo-pyrylium dye, nickel mercaptides complex in these dyestuffs.Have again, with the dyestuff of following general formula (a)-(f) expression, because photo-thermal conversion efficiency is good, so preferred.Particularly use the cyanines pigment of following general formula (a) expression, be used for of the present inventionly when making the image recording layer and use composition, can form the very big interaction with alkali soluble resins, and stable, economy is excellent, so the most preferred.

[changing 8]

R in the general formula (a) ¹And R ²Represent separately that respectively carbon number is the alkyl of 1-12, also can have substituting group on alkyl, these substituting groups can be selected from the group of being made up of alkoxyl, aryl, amide groups, alkoxy carbonyl, hydroxyl, sulfo group and carboxyl.Y ¹And Y ²Respectively separately expression oxygen, sulphur, selenium, dialkyl group methylene base or-CH=CH-.Ar ¹And Ar ²Represent aromatic hydrocarbyl respectively separately, also can have the substituting group of from the group of forming by alkyl, alkoxyl, halogen atom and alkoxy carbonyl, selecting, also available and Y ¹And Y ²Adjacent 2 continuous carbon atoms contract the aromatic rings ring.

Required equilibrium ion during X represents and during electric charge, X can not exist when the cationic moiety of pigment has anionic substituent.

Q represents the polymethine selected from the group of being made of three methines, five methines, seven methines, nine methines and 11 methines.From to when exposure used ultrared wavelength adaptability and stable aspect, five methines, seven methines or nine methines are more satisfactory, consider preferably have the cyclohexene ring that on either carbon, contains three continuous methine chains or have the cyclopentene ring from stability.

The also available group of selecting from the group of forming by alkoxyl, aryloxy group, alkylthio group, arylthio, dialkyl amino, diaryl amido, halogen atom, alkyl, aralkyl, cycloalkyl, aryl, hydroxyl, imines (イミニウ system) salt and with the substituting group of following general formula (2) expression of Q replaces.Can enumerate arylthios such as diaryl amido, thiophenyl such as halogen atom, diphenyl amido such as chlorine atom as desirable substituting group.

[changing 9]

R in the formula ³And R ⁴Represent separately that respectively hydrogen atom, carbon number are that alkyl or the carbon number of 1-8 is the aryl of 6-10, Y ³Expression oxygen atom or sulphur atom.

When being the infrared ray exposure of 800-840nm with wavelength, in the cyanines pigment with general formula (a) expression, seven methine cyanines pigments of the following general formula of the desirable especially usefulness enumerated (a-1) expression.

[changing 10]

In the general formula (a-1), X ¹Expression hydrogen atom or halogen atom.R ¹And R ²Represent separately that respectively carbon number is the alkyl of 1-12.Consider R from the storage stability of recording layer coating liquid ¹And R ²Be preferably carbon number at the alkyl more than 2, particularly preferably be R ¹And R ²Link mutually and form 5 Yuans rings or 6 Yuans rings.

Ar ¹And Ar ²Independent respectively expression aromatic hydrocarbyl also can have substituting group on it.Desirable aromatic hydrocarbyl can be enumerated phenyl ring and naphthalene nucleus.In addition, as desirable substituting group can enumerate carbon number at the alkyl below 12, halogen atom, carbon number at the alkoxyl below 12.Y ¹And Y ²Represent separately that respectively sulphur atom or carbon number are at the dialkyl group methylene base below 12.R ³And R ⁴Independent respectively expression carbon number also can have substituting group at the alkyl below 20 on it.Desirable substituting group can be enumerated carbon number in the alkoxyl below 12, carboxyl, sulfo group.R ⁵, R ⁶, R ⁷And R ⁸Independent respectively expression hydrogen atom or carbon number are at the alkyl below 12.Consider from the difficulty or ease program that raw material obtains, it is desirable to hydrogen atom.In addition, Z _a ^-Required balance anion in the expression and during electric charge is worked as R ¹-R ⁸In any when being replaced by anionic substituent, just no longer need Za ^-Consider desirable Za from the storage stability of recording layer coating liquid ^-For halogen ion, high chloro acid ion, tetrafluoro boric acid salt ion, hexafluorophosphoric acid salt ion and azochlorosulfonate acid ion, it is desirable to high chloro acid ion, tetrafluoro boric acid salt ion, hexafluorophosphoric acid salt ion and azochlorosulfonate acid ion especially.Applicable to temperature-sensitive eurymeric image recording layer, be specially adapted to thermosensitive type image recording layer with seven methine pigments of above-mentioned general formula (a-1) expression with the what is called interaction releasing type of alkali soluble resins collocation with phenol hydroxyl.

Among the present invention, object lesson as the cyanines pigment of using general formula (a) expression that can be suitable for, except that following illustrative example, also can enumerate the spy and open [0017]-[0019] section, spy in the 2001-133969 communique and open the pigment that [0012]-[0038] section, spy in the 2002-40638 communique opens record in [0012]-[0023] section in the 2002-23360 communique.

[changing 11]

[changing 12]

[changing 13]

As the infrared absorbent beyond above-mentioned, the available spy of having opens have a plurality of chromophoric dyestuffs, the spy that put down in writing in the 2001-242613 communique and opens 2002-97384 communique, United States Patent (USP) the 6th, 124, that puts down in writing in No. 425 specifications is connected with chromophoric pigment, United States Patent (USP) 6 with covalent bond on macromolecular compound, the anionic dye, the spy that put down in writing in 248, No. 893 specifications open dyestuff that the surface orientation base is arranged of putting down in writing in the 2001-347765 communique etc.

Among the present invention, as the pigment that infrared absorbent uses, can enumerate the pigment of record in commercially available pigment and colour index (C.I.) brief guide, " up-to-date pigment brief guide " (Japanese pigment technology association compiles, 1977 annuals), " up-to-date pigment applications technology " (CMC publishes, 1986 annuals), " the printing-ink technology " (CMC publishes, 1984 annuals).

As the kind of pigment, can enumerate black pigment, yellow uitramarine, orange colour pigment, brown pigments, red pigment, violet pigment, blue pigment, viridine green, fluorescent pigment, metal powder pigment, also have polymer in conjunction with pigment.Specifically, can use azoic dyes insoluble azo dyes, azo lake pigment, condensation azo dyes, chelating azo dyes, phthalocyanine pigment, anthraquinone class pigment, perylene and perynone class pigment, thioindigo class pigment, quinacridine class pigment, dioxazines pigment, isoindoline ketone pigment, Kui phthalein ketone pigment, dyeing mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment, carbon black etc.It is desirable to carbon black in these pigment.

These pigment are both available not surface treated, and are available through surface-treated yet.In the surface-treated method, can consider to adopt method with resin and wax coating surface, make method that surfactant adheres to, make method that reactive materials (as: organosilan coupling agent, epoxide, PIC etc.) combines with surface of pigments etc., above-mentioned surface treatment method is on the books in " character of metallic soap and application " (good fortune study), " printing-ink technology " (CMC publishes, 1984 annuals) and " up-to-date pigment applications technology " (CMC publishes, 1986 annuals).

The particle diameter of pigment is desirable in the scope of 0.01-10 μ m, be better in the scope of 0.05-1 μ m, is ideal especially in the scope of 0.1-1 μ m.During the particle diameter less than 0.01 μ m of pigment, disperse aspect thing stable in the image recording layer coating fluid not ideally sometimes, in addition, if surpass 10 μ m, then the uniformity aspect of image recording layer is not ideal sometimes.

As the method for dispersed color, can use the known dispersion technology that uses in printing ink preparation and the toner preparation etc.Can enumerate ultrasonic disperser, sand mill, vertical ball mill, particulate grinder (pearl mill), super grinder (super mill), ball mill, impeller dispersion machine (impeller), デスパ one ザ one, KD mill, colloid mill, dynatron, three-roll grinder, pressurization kneader etc. as dispersion machine.Detailed content is on the books in " up-to-date pigment applications technology " (CMC publication, 1986 annuals).

These pigment or dyestuff can add 0.01-50 quality % for all solids composition that constitutes recording layer, it is desirable to add 0.1-10 quality %, when adopting dyestuff, it would be desirable and add 0.5-10 quality %, when adopting pigment, it would be desirable and add 0.1-10 quality %.If the addition deficiency of pigment or dyestuff 0.01 quality % then has the speed downward trend,, then, can bring adverse effect to the uniformity of recording layer and the weatherability of recording layer along with the increase of addition if addition surpasses 50 quality %.In addition, dyestuff or pigment both can be single compounds, also can be the materials with the compound more than 2 kinds, for the exposure machine with several wavelength is complementary, also can and use different dyestuff or the pigment of absorbing wavelength.

(C) other composition

In the composition that image recording layer is used, as required, also can contain the cyclic acid anhydride, phenols, the organic acid that are useful on the raising speed; For obtain printing agent that visual picture adds after just finishing in exposure, as other filler etc. of the dye well of image colouring agent.

As cyclic acid anhydride United States Patent (USP) the 4th is arranged, 115, phthalic anhydride, tetrahydrophthalic anhydride, the hexahydro phthalic anhydride, 3 put down in writing in No. 128 specifications, 6-bridging oxygen-△ 4-tetrahydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, maleic anhydride, chloromaleic acid acid anhydride, α-phenyl maleic anhydride, succinic anhydride, pyromellitic acid dianhydride etc.

Can enumerate bisphenol-A, p-nitrophenol, p-thanatol, 2,3 as phenolic compound, 4-trihydroxybenzophenone, 4-dihydroxy benaophenonel, 2,4,4 '-trihydroxybenzophenone, 4,4 ', 4 "-trihydroxy-triphenyl methane, 4; 4 '; 3 ", 4 "-tetrahydroxy-3,5; 3 ', 5 '-tetramethyl triphenyl methane etc.

There is the spy to open clear 60-88942 communique as the organic acid compound, the sulfonic acid class of record in the Te Kaiping 2-96755 communique etc., the sulfinic acid class, the alkyl sulfide acids, phosphonic acid based, the phosphinic acids class, phosphoric acid ester, compounds such as carboxylic acids, specifically can enumerate the p-toluenesulfonic acid, DBSA, the p-toluenesulfinic acid, ethyl sulfuric acid, phenyl-phosphonic acid, phenyl phosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, M-phthalic acid, adipic acid, the p-toluic acid, 3, the 4-dimethoxybenzoic acid, phthalic acid, terephthalic acid (TPA), 1,4-cyclohexene-2, the 2-dicarboxylic acids, erucic acid, laurate, positive undecanoic acid, ascorbic acid etc.

Above-mentioned cyclic acid anhydride class, phenols, organic acid compound image recording layer with proportion in the composition with 0.05-15 quality % for well, serve as better with 0.1-5 quality %.

Can enumerate the photosensitive compounds that to emit acid through exposing and the composition that changes the organic dyestuff of tone with acid formation salt as the developer that makes visual picture after the exposure immediately.

The photosensitive compounds of emitting acid through exposure is the photolysis products that decomposes the compound that produces acidic materials through light.Can enumerate as: the spy opens o-naphthoquinones diazido-4-sulfamic acid halide of putting down in writing in the clear 50-36209 communique; The spy opens three halogenation methyl-2-, two pyrroles's ketones or the three halogenations methyl-s-triazine of putting down in writing in the clear 53-36223 communique; The spy opens various o-naphthoquinones two triazo-compounds of putting down in writing in the clear 55-62444 communique; The spy opens 2-three halogenations methyl-5-aryl-1,3 of putting down in writing in the clear 55-77742 communique, 4-oxadiazole compound; Diazol etc.

These compounds can be used alone or as a mixture, and its addition is desirable in the scope of 0.3-15 quality % for the gross mass of composition.

The organic dyestuff that forms salt with acid and can change tone is by interacting with above-mentioned photosensitive compounds, changing the organic dyestuff of its tone.

As such organic dyestuff, can use diphenylmethyl alkanes, triarylmethane class, thiazide, oxazine class, azophenlyene class, oxa anthracenes, anthraquinone class, imino group naphthoquinones class, azo methine class pigment.

Specifically can enumerate as bright green, eosin, ethyl violet, iodeosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyl triazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, diiodocosin, thymolsulfonphthalein, xylenol blue, methyl orange, IV orange, diphenyl sulfide be for carbazones, 2,7-dichlorofluorescein, paramethyl red, congo red, the plain 4B of benzopurpurin, α-Nai Hong, Nile blue-2B, Nile blue-A, Off エ Na セリ Application, crystal violet, malachite green, paramagenta, oil blue 603 ^#[オリエ Application ト chemical industry (strain) system], oil-bound distemper red 3 12 ^#[オリエ Application ト chemical industry (strain) system], oil red 5B[オリエ Application ト chemical industry (strain) system], oil scarlet 308 ^#[オリエ Application ト chemical industry (strain) system], oil red OG[オリエ Application ト chemical industry (strain) system], oil red RR[オリエ Application ト chemical industry (strain) system], glossy dark green 502 ^#[オリエ Application ト chemical industry (strain) system]; extraordinary supiron red BEH[hodogaya chemical industry (strain) system]; Victoria's pure blue B OH[hodogaya chemical industry (strain) system]; patent ethereal blue [Sumitomo three state's chemical industry (strain) system]; II the Sudan indigo plant [BASF AG's system]; m-cresols is purplish red; cresol red; rhodamine B; rhodamine 6G; fast acid violet R; the sulfonation rhodamine B; the Chinese scholartree Huang; 4-p-lignocaine phenyl imido grpup naphthoquinones; 2-carboxyl anilino--4-p-lignocaine phenyl imido grpup naphthoquinones; the hard esteramides base of 2-carbonyl-4-p-dihydroxy ethyl-amino-phenyl imine base naphthoquinones; p-methoxybenzoyl base-p '-lignocaine-o '-aminomethyl phenyl imido grpup acetanil; cyano group-p-lignocaine phenyl imido grpup acetanil; 1-phenyl-3-methyl-4-p-lignocaine phenyl imido grpup-5-pyrazolone; 1-betanaphthyl-4-p-lignocaine phenyl imido grpup-5-pyrazolone.

Desirable especially organic dyestuff is a triarylmethane class dyestuff.In triarylmethane class dyestuff, the useful especially dyestuff of putting down in writing, have sulfoacid compound in clear 62-2932471 communique, No. 2969021 communique of special permission of opening as the spy as balance anion.

These dyestuffs be used alone or as a mixture can, addition is preferably 0.3-15 quality % with respect to image recording layer with total composition.In addition as required also can with other dyestuff, pigment and usefulness, its use amount is preferably below the 70 quality % with respect to the total amount of dye well pigment, better is below the 50 quality %.

Image recording layer is with in the composition, for various purposes can contain various additives, as for the inking that improves image can contain the various resins of being with hydrophobic group, as the novolac resin of: octyl phenol-formaldehyde resin, tert-butyl benzene resinox, tert-butyl phenol-benzaldehyde resin, Abietyl modified novolac resin, these modifications-o-naphthoquinones diazido sulphonic acid ester etc.; In order to improve the flexible plasticizer that contains of filming, as: dibutyl phthalate, dioctyl phthalate, butyl glycolate, tricresyl phosphate, dioctyl adipate etc.Their addition, for the composition gross mass, in the scope of 0.01-30 quality % for well.

In order further to improve the wearability of filming, can make and contain known resin in the composition.Can enumerate as polyvinyl acetal resin, polyurethane resin, epoxy resin, vinyl chloride resin, nylon, mylar, acrylic resin as this resin.They can be used alone or as a mixture.The gross mass of the relative composition of addition, in 2-40 quality % scope for well.

In order to widen the tolerance of development, in composition, can add as the spy and open clear 62-251740 communique and special open the nonionic surface active agent, the spy that put down in writing in the flat 4-68355 communique and open clear 59-121044 communique and the special amphoteric surfactant of putting down in writing in the flat 4-13149 communique of opening.

As the object lesson of nonionic surface active agent, can enumerate polyethylene glycol and derivative class thereof, polyethylene glycol polypropylene glycol ether derivant class, polyethylene glycol polypropylene glycol block copolymer class, the polyethylene glycol alkyl ether class, polyethylene glycol polypropylene glycol alkyl ether, polyalkylene glycol alkyl phenyl ethers, the cithrol class, the polypropylene glycol fatty acid ester, the polyalkylene glycol alkyl amine, the amino ethers of polyalkylene glycol alkyl, the Polypropylene Glycol Glycerin Ether class, fatty acid glyceride and polyoxyethylene addition product class thereof, mountain multitude's dextranomer fatty acid ester and polyoxyethylene addition product class thereof, mountain multitude's sugar alcohol fatty acid ester and polyoxyethylene addition product class thereof, pentaerythritol fatty ester and polyoxyethylene addition product class thereof, glycerine borate fatty acid ester and polyoxyethylene addition product class thereof, fatty acid alkanol amides and polyoxyethylene addition product class thereof, the polyglyceryl fatty acid ester class, the polyoxyethylene addition product class of phytosterol, the polyoxyethylene addition product class of Off イトスノ one Le, the polyoxyethylene addition product class of vegetable oil, the polyoxyethylene addition product class of lanolin, the polyoxyethylene addition product class of lanolin alcohol, the polyoxyethylene addition product class of beeswax derivative, the polyoxyethylene addition product class of alkyl phenyl formaldehyde condensation products, the fluorine class surfactant of the acrylic compounds oligomer of band perfluor base etc. on the side chain.

Object lesson as amphoteric surfactant, can enumerate alkyl two (amino-ethyl) glycine, alkyl polyamino ethyl glycine hydrochloride, アモ one ゲ Application K (trade name, the first industrial pharmacy (strain) system, N-myristyl-N, N-three alkane ammonium carboxylic acid inner salt types), 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazole betaine, レボ Application 15 (trade name, Sanyo changes into (strain) system, alkyl imidazoline class).

Above-mentioned nonionic surface active agent and amphoteric surfactant image recording layer with ratio shared in the composition with 0.05-15 quality % for well, serve as better with 0.1-5 quality %.

In order to improve the quality of coated face, in composition, can contain surfactant, for example special fluorine class surfactant of putting down in writing in the clear 62-170950 communique of opening.

Desirable addition is the 0.001-1.0 weight % of total composition, and that better is 0.005-0.5 quality %.

Can contain weld in the composition.Be that the weld more than 70% of the absorbance at 436nm place serves as preferred wherein with the absorbance at 417nm place.

When using the preparation of compositions lithographic printing original, be arranged on as image recording layer on the support of above-mentioned lithographic printing plate-use by image recording layer.Image recording layer is dissolved or be dispersed in following a kind or mix in the organic solvent more than 2 kinds with composition, is applied to and carries out drying on the support.

Can use known compound as organic solvent, still,, select boiling point at 40-200 ℃, the solvent in 60-160 ℃ scope particularly from helping dry angle.

Can enumerate as: methyl alcohol, ethanol, just or isopropyl alcohol, just or alcohols such as isobutanol, diacetone alcohol as organic solvent; Ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, metacetone, DIBK, cyclohexanone, methyl cyclohexanone, acetylacetone,2,4-pentanedione; Hydro carbons such as benzene,toluene,xylene, cyclohexane, anisole; Ethyl acetate, acetic acid just or isopropyl ester, acetic acid just or acetates such as isobutyl ester, acetic acid ethyl butyl ester, capryl acetate; Halide such as carrene, dichloroethanes, monochloro-benzene; Ethers such as isopropyl ether, n-butyl ether, dioxane, dimethyl dioxane, oxolane; Ethylene glycol, glycol monomethyl ether, glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol (DEG) methyl ethyl ether, diethylene glycol diethyl ether, propane diols, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether, dihydroxypropane single-ether acetate, propylene glycol monobutyl ether, 3-methyl-polyalcohol and its derivatives such as 3-methoxybutanol; Methyl-sulfoxide, N, special solvents such as dinethylformamide.They can be used alone or as a mixture.The concentration of solid constituent is advisable with 2-50 quality % in the composition of coating.

(preparation of original edition of lithographic printing plate)

As the coating process of image recording layer, available as methods such as roller coat, dip-coating, airblade coating, engraved roll coating, heliogravure offset printing formula (gravure offset) coating, bucket type (hopper) coating, scraper (blade) coating, steel wire scraper (wire doctor) coating, sprayings with composition.Coating weight is in dried quality, with 0.3-4.0g/m ²For good.Along with the minimizing of coating weight, though it is little to make the light exposure of image, film-strength descends.Along with coating weight increases, need certain light exposure, but light-sensitive surface intensity is good, can improve anti-seal.

The image recording layer that is coated on the support normally carries out with hot-air with the drying of composition.Be heated to 30-200 ℃, particularly 40-140 ℃ scope is advisable.It is constant that baking temperature not necessarily will keep in drying, also can segmentation raise.In addition, the dry wind result that after dehumidification treatments, can obtain sometimes.The relative coated face of air of heating is with 0.1-30m/ second, particularly supply with the speed of 0.5-20m/ second and be advisable.

(back coating)

At the back side of support back coating is set as required.As this back coating, desirable available by the spy being opened the organic high molecular compound put down in writing in the flat 5-45885 communique and specially opening the overlay that metal oxide that the organo-metallic compound put down in writing in the flat 6-35174 communique or inorganic metal compound make through hydrolytie polycondensation is formed.In these overlays, Si (OCH ₃) ₄, Si (OC ₂H ₅) ₄, Si (OC ₃H ₇) ₄, Si (OC ₄H ₉) ₄Deng the low price of the alkyl oxide of silicon, obtain easily, and by these metal oxide coated layers that makes, its anti-development fluidity excellence, desirable especially.

[making of lithographic plate]

(exposure)

The above-mentioned original edition of lithographic printing plate that makes will carry out imaging exposure, development treatment usually.As the light source of the active ray of imaging exposure usefulness,, be preferably Solid State Laser, semiconductor laser especially to have light source for well from near-infrared to the region of ultra-red emission wavelength.

(developer solution)

The developer solution that is suitable for the development treatment of original edition of lithographic printing plate of the present invention is that pH is the developer solution of 9.0-13.5, and preferably pH is the developer solution of 10.0-13.2.(following title also contains " developer solution " that replenishes liquid to developer solution.) in available known in the past aqueous alkali.

Can enumerate as the salt of inorganic bases such as sodium metasilicate, potassium silicate, sodium phosphate, potassium phosphate, ammonium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium carbonate, potash, ammonium carbonate, sodium acid carbonate, saleratus, carbonic hydroammonium, Boratex, potassium borate, ammonium borate, NaOH, ammonium hydroxide, potassium hydroxide and lithium hydroxide.

In addition, also can enumerate methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, tri-isopropyl amine, n-butylamine, monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), second and embrace organic alkaline agents such as imines, ethylenediamine, pyridine.

These aqueous alkalis both can use a kind separately, also can will also use more than 2 kinds.

In the above-mentioned aqueous alkali, preferably use in fact the alkali-free metal silicate and contain the developer solution of the pH of nonreducing sugar and alkali as 9.0-13.5.If use the work of this developer solution (so-called " no silicate developer solution "), can prevent the generation of impurity and mud during development, so the stability of developer solution will improve greatly.In addition, surface that can the damage image recording layer and can make the inking of image recording layer maintain better good state.

In this developer solution,, contain at least a kind of nonreducing sugar and at least a kind of alkali as main component, and pH with 9.0-13.5 for well.

So-called nonreducing sugar is meant and does not contain free aldehyde radical and ketone group, do not show the carbohydrate of reproducibility.Specifically can be divided into the sugar alcohol of going back hydrogenating reduction on glucoside that original hase links to each other with non-carbohydrate and the carbohydrate of going back interconnected trehalose type compound sugar, carbohydrate between the original hase, which kind of all is suitable for.

Oligosaccharides as the trehalose type can be enumerated as sucrose, trehalose.

Can enumerate as alkyl glucoside, phenol glucoside, mustard oil glucoside as glucoside.

Can enumerate as D, L-arabitol, ribitol, xylitol, D, L-D-sorbite, D, L-mannitol, D, L-iditol, D, L-talitol, dulcitol (ズリシ Star ト) and Allit as sugar alcohol.

In addition, as nonreducing sugar, many alcohol that also applicable disaccharides hydrogenation makes and compound sugar hydrogenation make goes back substance (reduction malt sugar).

Wherein, desirable especially nonreducing sugar is that sugar alcohol, sucrose, reduction malt sugar, particularly D-D-sorbite, sucrose, reduction malt sugar have cushioning effect in suitable pH scope, and price is low, and is therefore preferred.

These nonreducing sugars can separately or will be used in combination more than 2 kinds, and their shared ratios in developer solution are good with 0.1-30 quality %, with 1-20 quality % for better.If concentration is low excessively, then can not obtain sufficient cushioning effect sometimes.If excessive concentration then is difficult to carry out highly enrichedization, in addition, cost can improve.

When reducing sugar and alkali are used in combination, As time goes on can become brown, pH also can descend gradually, therefore, can cause the decline of development property.

As with the alkali of nonreducing sugar combination, can use known in the past alkali.Can enumerate as the inorganic base of NaOH, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, tripotassium phosphate, triammonium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium carbonate, potash, ammonium carbonate, sodium acid carbonate, saleratus, carbonic hydroammonium, Boratex, potassium borate, ammonium borate etc.

Yet can enumerate methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, tri-isopropyl amine, n-butylamine, monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), second and embrace organic alkaline agents such as imines, ethylenediamine, pyridine.

These alkali can separately or will be used in combination more than 2 kinds.

It is desirable to NaOH, potassium hydroxide in them.Its reason is by regulate their consumption with respect to nonreducing sugar, can regulate pH in very wide pH scope.In addition, tri-sodium phosphate, tripotassium phosphate, sodium carbonate, potash etc. himself have cushioning effect, so also very desirable.

These alkali can be added into the pH of developer solution in the scope of 9.0-13.5, and its addition determines that according to the kind and the addition of desired pH and nonreducing sugar better pH scope is 10.0-13.2.

Also can use the alkaline buffer of forming by weak acid and highly basic except that carbohydrate in the developer solution.The weak acid of using as this buffer solution, with dissociation constant (pKa) 10.0-13.2 for well.

Select in the weak acid that such weak acid is put down in writing can waiting from " the IONISATIONCONSTANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION " of Pergamon press company distribution.

Can enumerate as: 2,2,3,3-tetrafluoro-1-propyl alcohol (pKa 12.74), trifluoroethanol (with 12.37), ethapon alcohols such as (with 12.24); Pyridine-2-aldehyde (with 12.68), pyridine-4-aldehyde aldehydes such as (with 12.05); Salicylic acid (with 13.0), 3-hydroxyl-2-naphthoic acid (with 12.84), catechol (with 12.6), gallic acid (with 12.4), sulfosalicylic acid (with 11.7), 3,4-dihydroxy sulfonic acid (with 12.2), 3,4-dihydroxy-benzoic acid (with 11.94), 1,2,4-trihydroxy benzene (with 11.82), quinhydrones (with 11.56), 1,2,3-benzenetriol (with 11.34), o-cresols (with 10.33), resorcinol (with 11.27), p-cresols (with 10.27), m-cresols (with 10.09) etc. have the compound of phenol hydroxyl; 2-diacetylmonoxime (with 12.45), acetoxime (with 12.42), 1,2-cycloheptaenedionedioxime (with 12.3), 2-hydroxy benzaldehyde oxime (with 12.10), dimethylglyoxime (with 11.9), oxalamide dioxime (with 11.37), acetophenone oxime oximes such as (with 11.35); The nucleic acid-related substance of adenosine (with 12.56), inosine (with 12.5), guanine (with 12.3), cytimidine (with 12.2), hypoxanthine (with 12.1), xanthine (with 11.9) etc.; Also have in addition, lignocaine methylphosphonic acid (with 12.32), 1-amino-3,3,3-trifluoro-benzoic acid (with 12.29), isopropylidene diphosphonic acid (with 12.10), 1,1-ethylene-diphosphonic acid (with 11.54), 1,1-ethylene-diphosphonic acid 1-hydroxyl (with 11.52), benzimidazole (with 12.86), thiobenzamide (with 12.8), picoline thioamides (with 12.5), barbituric acid weak acid such as (with 12.5).

It is desirable to sulfosalicylic acid, salicylic acid in these weak acid.As with the alkali of these weak acid combination, applicatory have NaOH, ammonium hydroxide, potassium hydroxide and a lithium hydroxide.These alkali can separately or will be used in combination more than 2 kinds.Above-mentioned various alkali can be adjusted to pH in the desirable scope according to concentration and combination and use.

To promote that developing performance, the dispersiveness that improves development impurity and the oleophylic China ink of galley image section are purpose, in developer solution, can add addition product, the surfactant of epoxides as required, organic solvent etc.

Can enumerate PEO sorbitan, PEO sorb furfuryl alcohol, PEO glycerine, PEO triethanolamine etc. as the addition product of epoxide.

Can enumerate the surfactant of anionic species, cationic, nonionic class and both sexes as desirable surfactant.

As the desirable example of surfactant, can enumerate the polyethylene oxide alkyl ethers class, PEO alkyl phenyl ethers, the polystyrene-based phenyl ethers of PEO, PEO PPOX alkyl ether, glycerin fatty acid moieties ester class, sorbitol anhydride fatty acid part ester class, pentaerythrite fat acid moieties ester class, the propane diols fatty acid monoester, sucrose-fatty part ester class, PEO sorbitol anhydride fatty acid part ester class, PEO D-sorbite fatty acid part ester class, the cithrol class, polyglycerol fatty acid part ester class, the polyoxyethylenated castor oil class, PEO glycerin fatty acid moieties ester class, the fatty diglycollic amide class, N, N-pair-2-hydroxy alkyl amine, the PEO alkylamine, the triethanolamine fatty acid ester, non-ionic surface active agents such as trialkyl amination oxygen;

Fatty acid salt, the rosin acid salt, hydroxyl alkane sulfonic acid salt, the alkane sulfonic acid salt, dialkyl sulfosuccinate succinate salt, the linear alkylbenzene sulfonate (LAS) class, the branch-alkylbenzene sulfonate class, the alkyl naphthalene sulfonic acid salt, alkyl phenoxy PEO propyl sulfonic acid salt, PEO alkyl sulfo group phenyl ether salt, N-methyl-N-oleyl taurine sodium salt, N-salts of alkyl sulfosuccinates monamide disodium salt, the mahogany acid salt, the sulfuric acid tallow oil, the sulfuric ester salt of fatty acid alkyl esters, the alkyl sulfate salt, polyethylene oxide alkyl ethers sulfuric ester salt, glycerine monofatty ester sulfuric ester salt, PEO alkyl phenyl ether sulfuric ester salt, PEO styryl phenyl ether sulfuric ester salt, the alkyl phosphate salt, the polyethylene oxide alkyl ethers phosphates, PEO alkyl phenyl ether phosphates, the partly-hydrolysed thing class of phenylethylene/maleic anhydride copolymer, the partly-hydrolysed thing class of alkene/copolymer-maleic anhydride, anion surfactants such as naphthalene sulfonate formalin condensation product class;

The cationic surfactant of quaternary ammonium salts such as alkylamine salt, TBuA bromine, PEO alkylamine salt, polyethylene polyamine derivative etc.;

Amphoteric surfactantes such as carboxybetaine class, amino acids, sulfobetaines class, amidosulphuric acid ester class, imidazolines.

In the above listed surfactant, " PEO " also can become " polyoxyalkylene " of polyoxymethylenes, PPOX, polybutylene oxide etc., also comprises these surfactants.

Better surfactant is the fluorine class surfactant that molecule contains perfluoroalkyl.Can enumerate as anionics such as perfluoroalkyl carboxylate, perfluoro alkyl sulfonic acid salt, perfluoroalkyl phosphates as fluorine class surfactant; Amphoteric such as perfluoroalkyl betaine; Perfluoroalkyl front three ammonium salts etc. are cationic; Perfluoroalkyl amine oxide, perfluoroalkyl ethylene oxide adduct, contain perfluoroalkyl and hydrophilic radical oligomer, contain perfluoroalkyl and lipophile group oligomer, contain perfluoroalkyl, hydrophilic radical and lipophile group oligomer, contain the nonionic of the urethane etc. of perfluoroalkyl and lipophile group.

Above-mentioned surfactant can separately or will be used in combination more than 2 kinds, adds 0.001-10 weight % in developer solution, preferably adds 0.01-5 quality % scope.

In developer solution, can use various stable developing agent.Can enumerate salt compounded of iodine such as tetraalkylammonium salt, 4-butyl-phosphonium bromide phosphonium salt and diphenyl iodine chloride such as polyethylene glycol addition product that the spy opens the sugar alcohol of putting down in writing in the flat 6-282079 communique, TBuA hydroxy salt as desirable example.

Can enumerate also that the spy opens the anion surfactant put down in writing in the clear 50-51324 communique or amphoteric surfactant, the spy opens the water-soluble cationic polymer, the spy that put down in writing in the clear 55-95946 communique and opens the water miscible Amphiphatic high polymer electrolyte of putting down in writing in the clear 56-142528 communique.

Also can enumerate addition that the spy opens clear 59-84241 communique has the organoboron compound of aklylene glycol, the spy opens the water soluble surfactant active of the poly-ethylene oxide block aggretion type PPOX block polymerization type of putting down in writing in the clear 60-111246 communique, the spy opens the replacement PEO of clear 60-129750 communique or the alkylene diamine compound of PPOX, it is polyethylene glycol more than 300 that the spy opens the weight average molecular weight of putting down in writing in the clear 61-215554 communique, the spy opens the fluorine-containing surfactant with cationic group of clear 63-175858 communique, soluble epoxide ethane addition product that the acid of Te Kaiping 2-39157 communique or the pure upward oxirane of addition more than 4 moles obtain and water-soluble poly alkylidene compound etc.

As organic solvent, applicable solubility to water is about the material below the 10 weight %, it is desirable to select the material below 5 quality %.Can enumerate as 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propyl alcohol, 4-phenyl-1-butanols, 4-phenyl-2-butanols, 2-phenyl-1-butanols, 2-phenoxetol, 2-BOE, o-methoxy-benzyl alcohol, m-methoxy-benzyl alcohol, p-methoxy-benzyl alcohol, benzylalcohol, cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol and 4 methyl cyclohexanol, N-phenylethanol amine and N-phenyldiethanol-amine etc.

The content of organic solvent is the 0.1-5 quality % of used liquid gross mass.The consumption of its use amount and surfactant is closely related, and along with the increase of organic solvent amount, the consumption that increases surfactant is for well.This is that then organic solvent can not dissolve fully because if the consumption of surfactant is few and the amount of organic solvent is used manyly, therefore, can not guarantee good development.

Also can add reducing agent in the developer solution.This is in order to prevent the pollution of galley.Can enumerate the amines of the oxybenzene compound, p-phenylenediamine (PPD), phenylhydrazine etc. of thiosalicylic acid, quinhydrones, Mitouer, methoxyl group benzoquinones, resorcinol, 2-methylresorcinol etc. as desirable organic reducing agent.Can enumerate sodium salt, sylvite, ammonium salt of inorganic acids such as sulfurous acid, Sulfite acid, phosphorous acid, phosphorus acid, thiosulfuric acid and hydrosulfurous acid etc. as better inorganic reducing agent.

In these reducing agents, what preventing polluting effect was special good is sulphite.When using these reducing agents,, it is desirable to contain 0.05-5 quality % with respect to developer solution.

Also can add organic carboxyl acid again in the developer solution.Desirable organic carboxyl acid is that carbon number is aliphatic carboxylic acid and the aromatic carboxylic acid of 6-20.Caproic acid, enanthic acid, sad, laurate, nutmeg acid, palmitic acid and stearic acid etc. are arranged, it is desirable to the alkanoic acid that carbon number is 8-12 especially as the object lesson of aliphatic carboxylic acid.In addition, unrighted acid, the branched carbochain acid that contains two keys in carbochain also can be used.As aromatic carboxylic acid phenyl ring is arranged, naphthalene nucleus, anthracene nucleus etc. are gone up by the compound of carboxyl substituted, specifically, the o-chlorobenzoic acid is arranged, the p-chlorobenzoic acid, the o-hydroxybenzoic acid, the p-hydroxybenzoic acid, the o-amino benzoic Acid, the p-amino benzoic Acid, 2,4-dicarboxyl benzoic acid, 2, the 5-dihydroxy-benzoic acid, 2, the 6-hydroxybenzoic acid, 2, the 3-dihydroxy-benzoic acid, 3, the 5-dihydroxy-benzoic acid, gallic acid, 1-hydroxyl-2-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 2-hydroxyl-1-naphthoic acid, the 1-naphthoic acid, 2-naphthoic acid etc., wherein hydroxynaphthoic acid especially effectively.

Water-soluble in order to improve, above-mentioned aliphatic and aromatic carboxylic acid are fit to be made into sodium salt or sylvite or ammonium salt to be used.Among the present invention in the used developer solution content to organic carboxyl acid do not have special restriction, still, if lower than 0.1 quality %, then effect is insufficient, in addition, if more than 10 quality %, then not only effect can not be further improved, also with other additive the time, its dissolving can be hindered on the contrary.Therefore, desirable addition is that in the scope of 0.1-10 quality %, that better is 0.5-4 quality % with respect to the developer solution that uses.

As required, also can contain anticorrisive agent, colouring agent, thickener, defoamer, water softener etc. in the developer solution.

Can enumerate as polyphosphoric acid and sodium salt thereof, sylvite and ammonium salt as water softener; Ethylenediamine tetra-acetic acid, diethylene-triamine pentaacetic acid, triethylenetetramine six acetate, hydroxyethylethylene diamine tri-acetic acid, nitrilotriacetic acid, 1,2-DACH tetraacethyl and 1,3-diaminourea-aminopolycanboxylic acid and their sodium salt, sylvite and ammonium salts such as 2-propyl alcohol tetraacethyl; Amino three (methylene phosphonic acids), ethylenediamine tetraacetic (methylene phosphonic acid), diethylentriamine five (methylene phosphonic acid), triethylenetetramine six (methylene phosphonic acid), AEEA three (methylene phosphonic acid), 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, their sodium salt, sylvite and ammonium salt etc.

This water softener can change its optimum amount according to the hardness of the hard water that is used for chelating and the variation of amount thereof, the consumption that it is common, the 0.01-5 quality % of the developer solution that is to use, the more preferably scope of 0.01-0.5 quality %.If addition is very little, then can not reach the purpose of interpolation fully, if too many, decolouring etc. will take place to the image section adverse influence.The remaining composition of developer solution is a water.The concentrate that developer solution is made water content in advance and lacked when using, dilute with water more in use, this helps transportation.The suitable enrichment of this moment is with the separation that do not cause each composition or to separate out be benchmark.

In order to promote to develop, improve the dispersiveness of development impurity and the oleophylic China ink of galley image section, also can in this developer solution, add above-mentioned various surfactants or organic solvent in case of necessity.

(post processing)

The lithographic plate that will carry out development treatment in above-mentioned developer solution and obtain, the opaquing fluid, protection glue etc. of making main composition with flushing water, the rinsing liquid that contains surfactant etc., Arabic gum, with starch derivatives carry out post processing.In the post processing of lithographic plate, these processing methods can be carried out various combinations and use.

(automatic processing machine)

In recent years, in masterplate and the press for the rationalization and the standardization of the operation that realizes making a plate, so the automatic processing machine that original edition of lithographic printing plate is used has obtained extensive employing.This automatic processing machine generally partly is made up of develop part and post processing, form by the device of carrying original edition of lithographic printing plate and each processing liquid bath and spray equipment, the original edition of lithographic printing plate along continuous straight runs of end exposure is transmitted, the various treatment fluids that will suct with pump are developed and post processing by the nozzle ejection of sprayer simultaneously.In addition, the method for following development and post processing is arranged also recently, be about to original edition of lithographic printing plate and be immersed in the groove that is full of treatment fluid,, transmit master and carry out the method for development treatment by the effects such as deflector roll in the liquid; With develop after a certain amount of a small amount of flushing water supply space of a whole page is washed the method that its waste water is utilized as the dilution water of developer solution stoste again.

In this automatic processing procedure, according to situations such as treating capacity and machine hours, can be on one side in the various treatment fluids additional additional liquid separately, Yi Bian handle.In fact the so-called disposable processing mode of handling with original treatment fluid is also applicable.

To be located on the printing machine through the lithographic plate that this processing makes, can be applicable to a large amount of printings.

[embodiment]

Specifically introduce the present invention with embodiment below, still, the present invention is not limited to these.

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

(support body for lithographic plate printing plate A)

Aluminium sheet (JIS A1050 material) to 0.3mm thickness carries out the various surface treatments of following (a)-(g) continuously, makes support body for lithographic plate printing plate A.After carrying out various processing and washing, use the roll mangle.

(a) alkaline etching is handled

With caustic soda concentration is that 30g/L, aluminium ion concentration are that 10g/L, temperature are 60 ℃ the aqueous solution, by sprayer the above-mentioned aluminium sheet that makes is carried out the etch processes in 10 seconds, makes every square metre of dissolving of aluminium sheet 0.5g.With sprayer wash thereafter.

(b) decontamination is handled

With temperature is that 30 ℃ concentration of nitric acid is the aqueous solution (aluminium ion that contains 10g/L) of 12g/L, carries out decontamination by sprayer and handles, and is washed by sprayer thereafter.

(c) electrochemistry asperities processing

Alternating voltage with 50Hz carries out the processing of electrochemistry asperities continuously.At this moment electrolyte is the aqueous hydrochloric acid solution (aluminium ion that contains 10g/L) of 15g/L, and temperature is 30 ℃.The waveform of AC power is sinusoidal wave, handles as electrode being carried out electrochemical surface with carbon electrode.What use as impressed current anode is ferrite.Electrolytic cell is with device shown in Figure 3.5% electric current from power supply is diverted on the impressed current anode.

Current density is 16A/dm at the peak value place of electric current ², the summation of the electric weight when electric weight is made anode with aluminium sheet is counted 400C/dm ²

With sprayer wash thereafter.

(d) alkaline etching is handled

With caustic soda concentration is that 36g/L, aluminium ion concentration are the aqueous solution of 10g/L, under 35 ℃, aluminium sheet is carried out the etch processes in 10 seconds by sprayer, make every square metre of dissolving of aluminium sheet 0.1g, removing what generate when alternating current with preceding operation carries out the processing of electrochemistry asperities then is the dirt of main component with aluminium hydroxide, the seamed edge of the hole of generation is partly dissolved, makes seamed edge partly become smooth.At last, wash by sprayer.

(e) decontamination is handled

With temperature is that 30 ℃, concentration are the aqueous sulfuric acid (aluminium ion that contains 10 quality %) of 15 quality %, carries out the decontamination in 10 seconds by sprayer and handles, and is washed by sprayer then.

(f) anodized

The anodic oxidation device that dc electrolysis is carried out in use carries out anodized, makes support body for lithographic plate printing plate.As the electrolyte of supplying with first and second electrolysis section, use sulfuric acid.Electrolyte is the sulfuric acid of concentration 10 quality % (aluminium ion that contains 5.0 quality %), and temperature is 20 ℃.Current density is 6A/dm ²Wash by sprayer then.The amount of final oxide-film is 2.5g/m ²

The surface roughness R of the support body for lithographic plate printing plate after anodized _aBe 0.44 μ m.

(g) alkali silicate is handled

It is that 20 ℃, concentration are 10 seconds in the treatment trough of No. 3 sodium silicate aqueous solutions of 1.0 quality % that support body for lithographic plate printing plate after the anodized is immersed in temperature, carries out alkali silicate and handles (silicate processing).By sprayer with well water wash thereafter.

(support body for lithographic plate printing plate B)

Except changing the current density in above-mentioned (c) into 12A/dm ², electric weight changes 300C/dm into ²In addition, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate B.The surface roughness R of the support body for lithographic plate printing plate after the anodized _aBe 0.34 μ m.

(support body for lithographic plate printing plate C)

Except changing the current density in above-mentioned (c) into 24A/dm ², electric weight changes 600C/dm into ²In addition, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate C.The surface roughness R of the support body for lithographic plate printing plate after the anodized _aBe 0.34 μ m.

(support body for lithographic plate printing plate D)

Except in above-mentioned (c), use electrolytic cell shown in Figure 2 instead and carry out the processing of electrochemistry asperities, and in above-mentioned (d), the temperature of the caustic soda aqueous solution is changed into beyond 30 ℃, other uses the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate D.

(support body for lithographic plate printing plate E)

Except in above-mentioned (c), use electrolytic cell shown in Figure 2 instead and carry out electrochemical asperities processing, and in above-mentioned (d), the temperature of the caustic soda aqueous solution is changed into beyond 45 ℃, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate E.

(support body for lithographic plate printing plate F)

Except in above-mentioned (g), the concentration of No. 3 sodium silicate aqueous solutions is changed into beyond the 0.2 quality %, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate F.

(support body for lithographic plate printing plate G)

Except in above-mentioned (g), change the concentration of No. 3 sodium silicate aqueous solutions into 2.5 quality % and temperature is changed into beyond 50 ℃, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate G.

(support body for lithographic plate printing plate H)

Except in above-mentioned (c), change current density into 12A/dm ², electric weight changes 50C/dm into ²In addition, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate H.The surface roughness R of the support body for lithographic plate printing plate after the anodized _aBe 0.24 μ m.

(support body for lithographic plate printing plate I)

Except in above-mentioned (g), with the concentration of No. 3 sodium silicate aqueous solutions change 2.5 quality % into, temperature is made as beyond 80 ℃, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate I.

(support body for lithographic plate printing plate J)

Except the processing of not carrying out above-mentioned (g) operation, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate J.

(support body for lithographic plate printing plate K)

Except in above-mentioned (d) temperature of the caustic soda aqueous solution being made as 60, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate K.

(support body for lithographic plate printing plate L)

Except successively by following (h), (i) and (j) operation handle above-mentioned to replace (a) and (b) the operation, all the other use the method same with preparing support body for lithographic plate printing plate A to make support body for lithographic plate printing plate L.The surface roughness R of the support body for lithographic plate printing plate after the anodized _aBe 0.55 μ m.

(h) mechanical asperities processing

Use device shown in Figure 1, will as the suspension (proportion 1.12) of the grinding agent (silica sand) of grinding milk and water supply with the surface of aluminium sheet on one side, carry out mechanical asperities processing with the roller shape nylon bruss that rotates on one side.The average grain diameter of grinding agent is 8 μ m, and maximum particle diameter is 50 μ m.The material of nylon bruss is a NYLON610, and the diameter of staple length 50mm, hair is 0.3mm.Perforate on the tube of the stainless steel of φ 300mm is closely implanted the bristle of nylon bruss wherein.Rotating brush is with three.The distance of two backing rolls (φ 200mm) of brush bottom is 300mm.Make 7kW more than the load before the duty ratio brush roller of CD-ROM drive motor of the brush rotation of brush roller is pushed aluminium sheet.The direction of rotation of brush is identical with the moving direction of aluminium sheet.The rotation number of brush is 200rpm.

(i) alkaline etching is handled

With caustic soda concentration is 26 quality %, and aluminium ion concentration is that 6.5 quality %, temperature are 70 ℃ the aqueous solution, by sprayer the above-mentioned aluminium sheet that makes is carried out the etch processes in 10 seconds, makes every square metre of dissolving of aluminium sheet 6g.Wash with sprayer then.

(j) decontamination is handled

With temperature is that 30 ℃, concentration of nitric acid are the aqueous solution (aluminium ion that contains 0.5 quality %) of 1 quality %, carries out decontamination by sprayer and handles, and is washed by sprayer thereafter.

(support body for lithographic plate printing plate M)

Except being that the aphrolite of 150 μ m replaces silica sand to make grinding agent with average grain diameter 50 μ m, maximum particle diameter in above-mentioned (h), the rotation number of brush is made as 250rpm, and in above-mentioned (i), the meltage of aluminium is made as 8g/m ², with following (k), (l) and (m) operation replace above-mentioned (c), (d) and (e) beyond the operation, all the other use the method same with preparing support body for lithographic plate printing plate L to make support body for lithographic plate printing plate M.The surface roughness R of the support body for lithographic plate printing plate after the anodized _aBe 0.55 μ m.

(k) electrochemistry asperities processing

Alternating voltage with 60Hz carries out electrochemical asperities processing continuously.At this moment electrolyte is that concentration of nitric acid is the aqueous solution (aluminium ion that contains 5g/L) of 10.5g/L, and temperature is 50 ℃.The waveform of AC power is a waveform shown in Figure 5, and current value is 0.8msec from the zero time T P to peaking, duty ratio 1: 1, with trapezoidal square wave ac, with carbon electrode as electrode being carried out the processing of electrochemistry asperities.As the impressed current anode ferrite.Electrolytic cell is with device shown in Figure 4.5% electric current from power supply is divided on the impressed current anode.

Current density is 30A/dm at the peak value place of electric current ², the summation of the electric weight when electric weight is anode with the aluminium sheet is counted 220C/dm ²

Then, wash by sprayer.

(l) alkaline etching is handled

With caustic soda concentration is that 26 quality %, aluminium ion concentration are the aqueous solution of 6.5 quality %, under 60 ℃, by sprayer aluminium sheet is carried out etch processes, make every square metre of dissolving of aluminium sheet 1.0g, removing what generate when alternating current with preceding operation carries out the processing of electrochemistry asperities is the dirt composition of principal component with aluminium hydroxide, and the seamed edge with the hole that generates is partly dissolved again, makes seamed edge partly become smooth, afterwards, wash by sprayer.

(m) decontamination is handled

With temperature is that 30 ℃, sulfuric acid concentration are the aqueous solution (aluminium ion that contains 4.5 quality %) of 15 quality %, carries out decontamination by sprayer and handles, and is washed by sprayer thereafter.

(support body for lithographic plate printing plate N)

Except the temperature of the caustic soda aqueous solution being made as 32 ℃ without above-mentioned (h) operation and in above-mentioned (l), the meltage of aluminium being made as 0.2g/m ²In addition, use the method same to make support body for lithographic plate printing plate N with preparing support body for lithographic plate printing plate M.The surface roughness R of the support body for lithographic plate printing plate after the anodized _aBe 0.25 μ m.

2. the mensuration of support body for lithographic plate printing plate surface configuration

The hole on the above-mentioned lithographic printing plate surface that makes is carried out the mensuration of following (1)-(3).

The results are shown in the table 1."-" represents the not hole of this average pore size in the table 1.

(1) average pore size of big hole

With SEM with 1000 times enlargement ratio from directly over the support surface is taken, in the SEM photo that obtains, extract the big hole that is linked to be ring-type around 50 holes out, read its diameter as the aperture, and calculate average pore size.

(2) average pore size of little hole

Use high-resolution SEM, with 50000 times enlargement ratios from directly over the support surface is taken, in the SEM photo that obtains, extract 50 little anti-caves out, read its diameter as the aperture, and calculate average pore size.

(3) degree of depth is to the mean value of the ratio in foveola aperture

The degree of depth is to the mean value of the ratio in foveola aperture, be with 50000 times enlargement ratio the cross section of support to be taken with high-resolution SEM, 20 apertures of extraction are the foveola below the 0.8 μ m in the SEM photo that obtains, and read the aperture and the degree of depth, ask its ratio calculating mean value.

3. the calculating of support body for lithographic plate printing plate surface sharp factor

△ S is asked on the above-mentioned support body for lithographic plate printing plate surface that makes as follows ⁵⁰

The results are shown in the table 1.

(1) measures surface configuration with atomic force microscope

Measure surface configuration with atomic force microscope (SP 13700, Seiko electronics industry society system), ask for three-dimensional data.Introduce concrete determination step below.

Cut the support body for lithographic plate printing plate of 1cm square size, place it on the horizontal sample platform of piezoelectric scanner, make cantilever near sample surfaces, when arriving regional that active force begins to have an effect between atom, carry out the scanning on the XY direction, at this moment, read the concavo-convex degree of sample with the displacement of piezoelectricity on the Z direction.Piezoelectric scanner can be used on the scanner that can scan 150 μ m on the XY direction, can scan 10 μ m on the Z direction.The cantilever resonant frequency is 120-150kHz, and spring constant is the cantilever (AC-160TS, Olympus society system) of 12-20N/m, and measures with DFM type (Dynamic ForceMode).In addition, by the three-dimensional data of asking for being suitable for the slightly little inclination of least square approximation method correcting sample, ask for datum level.

During apparatus measures, 50 μ m on the surface ²Square frame in measure 512 * 512 points.The resolution ratio of XY direction is 1.9 μ m, and the resolution ratio of Z direction is 1nm, and sweep speed is 60 μ m/sec.

(2) △ S ⁵⁰Calculating

(f (x, y)) extracts 3 adjacent points out, obtains the summation of the small triangle area that is formed by these 3 points, obtains real area S with 3 dimension data of trying to achieve in above-mentioned (1) _x ⁵⁰Difference in surface area △ S ⁵⁰By calculate real area S _x ⁵⁰The area S of Ce Dinging geometrically _o ⁵⁰, obtain by above-mentioned formula (1).

4. the mensuration of Si atom adhesion amount on the support body for lithographic plate printing plate surface

Use fluorescent x-ray analyzer, measure the Si atom adhesion amount on each support body for lithographic plate printing plate surface by calibration curve method.The results are shown in the table 1.Value in the table 1 has comprised the amount of the Si atom that contains in the aluminium sheet.

As the standard specimen of production standard curve, be used in φ on the aluminium sheet and be in the area of 30mm and drip the sodium silicate aqueous solution that contains known quantity Si atom equably and make its dried sample.The condition of x-ray fluorescence analysis is as follows.

Fluorescent x-ray analyzer: electric machine industry of science society system RIX 300, X-ray tube ball: Rh, measure spectrum: Si-K α, tube voltage: 50kV, tube current: 50mA, slit: COARSE, spectrum crystallization: RX4, detector: F-PC, analyze area: 30mm φ, peak position (2 θ): 144.75deg., background line (2 θ): 140.70deg. and 146.85deg., accumulated time: 80 seconds/sample.

5. the preparation of original edition of lithographic printing plate

(embodiment 1-7 and comparative example 1-7)

The following temperature-sensitive eurymeric image recording layer that is provided with on above-mentioned each support body for lithographic plate printing plate that makes makes the original edition of lithographic printing plate of embodiment 1-7 shown in the table 1 and comparative example 1-7.Before image recording layer is set, priming coat described later is set.

The priming coat liquid of the following composition of coating in 80 ℃ of following dry 15 seconds, is made priming coat and is filmed on support body for lithographic plate printing plate.The amount of being coated with of filming after the drying is 15mg/m ²

(priming coat liquid composition)

Following macromolecular compound 0.3g

Methyl alcohol 100g

Water 1g

Change 14

Then, modulate the heat sensing layer coating fluid of following composition, it is coated on the support of the lithographic printing plate-use that is provided with priming coat, make the dried coating weight of this heat sensing layer coating fluid (heat sensing layer coating weight) reach 1.8g/m ², drying forms heat sensing layer (temperature-sensitive eurymeric image recording layer), makes original edition of lithographic printing plate.

(composition of heat sensing layer coating fluid)

Novolac resin (m-cresols/p-cresols=60/40, weight average molecular weight are 7000, contain unreacted cresols 0.5 quality %) 0.90g

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

The cyanine dyes A 0.1g that represents with following structural formula

Tetrahydrophthalic anhydride 0.05g

P-methyl benzenesulfonic acid 0.002g

The equilibrium ion of ethyl violet is made as the material 0.02g of 6-hydroxy-beta-naphthalene sulfonic acids

Fluorine class surfactant (デイ Off エ Application サ F-780F, big Japanese ink chemical industry society system, solids content 30 quality %) 0 0.0045g (being scaled solid)

Fluorine class surfactant (デイ Off エ Application サ F-780F, big Japanese ink chemical industry society system, solids content 100 quality) 0.035g

Butanone 12g

[changing 15]

Cyanine dyes A

6. the evaluation of original edition of lithographic printing plate

Estimate speed and the anti-seal of lithographic plate, anti-seal (the anti-seal of roasting version), the resistance to soiling after the roasting version processing and the complexity of observing the shinny state of the space of a whole page of the above-mentioned original edition of lithographic printing plate that makes with following method.

(1) speed

With the original edition of lithographic printing plate that the makes TrendSetter with the Creo corporate system, the roller rotary speed with 150rpm changes beam intensity between 2-13W, carry out image scanning (image record).

With the PS automatic processing machine 940H of Fujiphoto (strain) system of pack the alkaline developer A of following composition and any developer solution in B, keep the condition of liquid temperature 30 ℃ under development 20 seconds thereafter.Use alkaline developer A among the embodiment 6, use alkaline developer B in other embodiment and the comparative example.The pH of alkaline developer A is 13.2, the pH of alkaline developer B is 13.3.

Pollution that causes according to the residual film that does not take place because of the image recording layer of poor visualization or beam intensity painted and can develop well the time are estimated speed.The more little speed of beam intensity is high more.The results are shown in the table 1.

(composition of alkaline developer A)

SiO ₂K ₂O (K ₂O/SiO ₂=1/1 (mol ratio)) 4.0 quality %

Citric acid 0.5 quality %

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

Water 95.0 quality %

(composition of alkaline developer B)

D-D-sorbite 2.5 quality %

NaOH 0.85 quality %

Water 96.15 quality %

(2) anti-seal

Be to carry out image scanning under the condition of 10W with the roller rotary speed of 150rpm with the original edition of lithographic printing plate that makes in beam intensity with the TrendSetter of Creo society system.

Afterwards with the PS automatic processing machine 940H of Fujiphoto (strain) system of any alkaline developer among above-mentioned alkaline developer A and the B of packing into, keeping the liquid temperature is the 20 seconds kinds of developing under 30 ℃ the condition, makes lithographic plate.Use alkaline developer A among the embodiment 6, use alkaline developer B in other embodiment and the comparative example.

With the リスロ Application printing machine of lithographic printing plate-use Omori Corp. system of making, print with DIC-GEOS (N) black ink of big Japanese ink chemical industry society system, judge that with the naked eye the printing number that the density of image on the spot begins when thin out estimates anti-seal.The results are shown in the table 1.

(3) the anti-seal after roasting version is handled

The space of a whole page of the lithographic plate that makes according to method identical when estimating anti-seal with the roasting plate shaving lotion BC-3 wiping of Fujiphoto (strain) system, under about 240 ℃, the roasting plate that carried out 7 minutes is handled.Wash then, water dilutes 2 times with the glue GU-7 of Fujiphoto (strain) system, handles the space of a whole page with this liquid again.

Thereafter, the same during with the anti-seal of evaluation, リスロ Application printing machine with Omori Corp.'s system, DIC-GEOS (N) black ink with big Japanese ink chemical industry society system is printed, judge that with the naked eye the density of image on the spot begins the printing number when thin out, estimates the anti-seal (the roasting anti-seal of plate) after roasting plate is handled.The results are shown in the table 1.

(4) resistance to soiling

The lithographic plate that employing makes according to method identical when estimating anti-seal, with the ダイヤ of Mitsubishi type F2 printing machine (Mitsubishi Heavy Industries Ltd industry society system), and use DIC-GEOS (S) chilli oil China ink to print, with the naked eye estimate the pollution condition of 10,000 back roll cylinder-packings of printing.

The results are shown in the table 1.The pollution of cylinder dressing uses zero from less to more respectively, △, * Three Estate estimates.

(5) performance of the shinny state complexity of the observation space of a whole page

The lithographic plate that will make according to method identical when estimating anti-seal is contained on the リスロ Application printing machine of Omori Corp.'s system, increase the quantity delivered of fountain solution on one side, the bright situation of the non-image part on the space of a whole page of detecting by an unaided eye is on one side tested an edition property (observing the complexity of the shinny state of the space of a whole page) with the quantity delivered evaluation that just begins the fountain solution when shinny.

The results are shown in the table 1.According to the quantity delivered that just begins the fountain solution when shinny from how to few, with zero, △, * Three Estate estimates.

By can being clear that in the table 1, original edition of lithographic printing plate of the present invention (embodiment 1-7) its speed and resistance to soiling, anti-seal when making lithographic plate and to observe the performance of complexity of the shinny state of the space of a whole page all very excellent.

Have in addition in the original edition of lithographic printing plate of the present invention (embodiment 1-7) of the image recording layer that contains the above novolac resin of 30 quality %, except that above-mentioned characteristic, the anti-seal of its roasting version is also excellent.

Have again, after the exposure, when the pH that promptly uses alkali-free metal silicate in fact and contain nonreducing sugar and alkali develops as the developer solution of 9.0-13.5 (embodiment 1-5 and 7), also can make speed, resistance to soiling, anti-seal and observe all excellent lithographic plate of performance of the complexity of the shinny state of the space of a whole page.

Table 1

	The average pore size (μ m) of big hole	The average pore size of little hole (μ m)	The degree of depth is to the mean value of the ratio in the aperture of little hole	Difference in surface area △ S ⁵⁰(％)	Adhesion amount (the mg/m of Si atom ²)	Speed (W)	Anti-seal (ten thousand)	Roasting version anti-seal (ten thousand)	Resistance to soiling	Observe the complexity of the shinny state of the space of a whole page
	The average pore size (μ m) of big hole	The average pore size of little hole (μ m)		Difference in surface area △ S ⁵⁰(％)	Adhesion amount (the mg/m of Si atom ²)	Speed (W)	Anti-seal (ten thousand)	Roasting version anti-seal (ten thousand)	Resistance to soiling		Embodiment 1	?5	?0.2	?0.34	?30	?4.0	?4.0	?5	?15	?○	?○
Embodiment 2	?2	?0.2	?0.34	?27	?4.0	?4.5	?5	?15	?○	?○	Embodiment 1	?5	?0.2	?0.34	?30	?4.0	?4.0	?5	?15	?○	?○
Embodiment 2	?2	?0.2	?0.34	?27	?4.0	?4.5	?5	?15	?○	?○	Embodiment 3	?8	?0.2	?0.34	?35	?4.0	?4.0	?5	?15	?○	?○
Embodiment 4	?5	?0.05	?0.60	?40	?4.0	?4.0	?5	?15	?○	?○	Embodiment 3	?8	?0.2	?0.34	?35	?4.0	?4.0	?5	?15	?○	?○
Embodiment 4	?5	?0.05	?0.60	?40	?4.0	?4.0	?5	?15	?○	?○	Embodiment 5	?5	?0.6	?0.20	?20	?4.0	?4.0	?4.5	?15	?○	?○
Embodiment 6	?5	?0.2	?0.34	?30	?2.0	?4.0	?5	?15	?○	?○	Embodiment 5	?5	?0.6	?0.20	?20	?4.0	?4.0	?4.5	?15	?○	?○
Embodiment 6	?5	?0.2	?0.34	?30	?2.0	?4.0	?5	?15	?○	?○	Embodiment 7	?5	?0.2	?0.34	?30	?15.0	?4.0	?4.5	?15	?○	?○
Comparative example 1	?-	?0.2	?0.34	?15	?4.0	?4.0	?5	?15	?○	?×	Embodiment 7	?5	?0.2	?0.34	?30	?15.0	?4.0	?4.5	?15	?○	?○
Comparative example 1	?-	?0.2	?0.34	?15	?4.0	?4.0	?5	?15	?○	?×	Comparative example 2	?5	?0.2	?0.34	?30	?17.0	?4.0	?1	?5	?○	?○
Comparative example 3	?5	?0.2	?0.34	?30	?0.0	?10.0	?6	?17	?×	?○	Comparative example 2	?5	?0.2	?0.34	?30	?17.0	?4.0	?1	?5	?○	?○
Comparative example 3	?5	?0.2	?0.34	?30	?0.0	?10.0	?6	?17	?×	?○	Comparative example 4	?5	?0.9	?0.10	?28	?4.0	?4.0	?3	?5	?○	?○
Comparative example 5	?12	?0.2	?0.34	?30	?4.0	?9.0	?6	?15	?△	?○	Comparative example 4	?5	?0.9	?0.10	?28	?4.0	?4.0	?3	?5	?○	?○
Comparative example 5	?12	?0.2	?0.34	?30	?4.0	?9.0	?6	?15	?△	?○	Comparative example 6	?15	?1.2	?0.10	?23	?4.0	?4.0	?3	?5	?△	?○
Comparative example 7	?-	?1.0	?0.70	?45	?4.0	?4.0	?6	?15	?△	?×	Comparative example 6	?15	?1.2	?0.10	?23	?4.0	?4.0	?3	?5	?△	?○

As mentioned above, original edition of lithographic printing plate of the present invention, its speed and the resistance to soiling when making lithographic plate, anti-seal and to observe the performance of complexity of the shinny state of the space of a whole page all excellent.

Claims

1. original edition of lithographic printing plate, it is the master that support body for lithographic plate printing plate is provided with the lithographic plate that image recording layer that effect by heat can form image forms, and the support of this lithographic printing plate-use is to the aluminium sheet electrochemistry asperities processing that contains aqueous solution of hydrochloric acid at least, anodized and alkali silicate are handled and are made, it is characterized in that, described support body for lithographic plate printing plate have from the teeth outwards by average pore size be 2-10 μ m big hole peace all the aperture be the overlapping Grains shape that constitutes of little hole of 0.05-0.8 μ m, and, mean value with respect to the ratio of the degree of depth in aperture, described pitting cave is 0.2-0.6

For the support of described lithographic printing plate-use, measure surperficial 50 μ m with atomic force microscope ²512 * 512 points in the square frame obtain three-dimensional data, and try to achieve real area S by this three-dimensional data according to approximate line-of-sight course _x ⁵⁰, again by real area S _x ⁵⁰The area S of Ce Dinging geometrically _o ⁵⁰, press following formula (1)

△S ⁵⁰＝(S _x ⁵⁰-S _o ⁵⁰)/S _o ⁵⁰×100(％)??????????????????(1)

The difference in surface area △ S that tries to achieve ⁵⁰Be 20-40%, the lip-deep Si atom adhesion amount of described support body for lithographic plate printing plate is 1.0-15.0mg/m ²

2. original edition of lithographic printing plate as claimed in claim 1 is characterized in that described image recording layer contains the above novolac resin of 30 quality %.

3. the preparation method of a lithographic plate, after it is characterized in that original edition of lithographic printing plate to claim 1 or 2 exposes, the pH that contains nonreducing sugar and alkali with in fact not containing alkali silicate is that the developer solution of 9.0-13.5 develops, and makes lithographic plate.