CN100551716C - Exposure visible image formation method, aluminum support and the planographic printing plate material of planographic printing plate material - Google Patents

Exposure visible image formation method, aluminum support and the planographic printing plate material of planographic printing plate material Download PDF

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Publication number
CN100551716C
CN100551716C CNB2006800032769A CN200680003276A CN100551716C CN 100551716 C CN100551716 C CN 100551716C CN B2006800032769 A CNB2006800032769 A CN B2006800032769A CN 200680003276 A CN200680003276 A CN 200680003276A CN 100551716 C CN100551716 C CN 100551716C
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China
Prior art keywords
printing plate
plate material
planographic printing
image formation
exposure
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CN101107136A (en
Inventor
河村朋纪
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Konica Minolta Medical and Graphic Inc
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Konica Minolta Medical and Graphic Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Materials For Photolithography (AREA)

Abstract

The object of the present invention is to provide a kind of exposure visible image formation method of planographic printing plate material, it is in the printing of planographic printing plate material, but can give on the machine exposure visible image formation method of developing, test the planographic printing plate material of the printing process that edition property is good, good, the anti-seal of colorrendering quality is good.This method comprises, make planographic printing plate material carry out image exposure, and formation visual image, described planographic printing plate material comprises the image formation layer on aluminum support and the aluminum support, the surface of described aluminum support has the anodic oxidation coating pore, and described aluminum support has the coloured material of the generation change color of being heated in its anodic oxidation coating pore.

Description

Exposure visible image formation method, aluminum support and the planographic printing plate material of planographic printing plate material
Technical field
The present invention relates to planographic printing plate material and exposure visible image formation method thereof, (コ Application ピ ユ--ト ウ-プ レ-ト) (CTP) mode can form the exposure visible image formation method of the planographic printing plate material of image especially to relate to the employing computer master making.
Technical background
Now,,, developed and adopted the CTP mode to print, but this print request is inexpensive, operate easily and have and the CTP mode printing plate material of the printing adaptability that so-called PS version in the past is equal along with the digitlization of printed image data at print field.
Especially, as everyone knows, require in recent years not need to use and contain special drug material (alkali for example, acid, the development treatment of treatment fluid solvent etc.), and applicable to the printing plate material of in the past printing machine, for example, the printing plate material that does not need the phase-change type of development treatment fully, make water or based on the printing plate material that neutral treatment fluid is handled that comes down to of water, the initial stage of printing on printing machine is carried out the printing plate material that development treatment does not especially need the printing plate material etc. of developing procedure to be called no chemicals type printing plate material or exempts from processing type printing plate material.
The above-mentioned printing plate material of exempting from the processing type that does not need the printing plate material of development treatment fully or on printing machine, develop since after exposure, carry out when being installed on the printing machine required punching (パ Application チ Application グ), so and PS in the past similarly must have so-called exposure visible image.
In addition, it is main during the image of exempting from the printing plate material of processing type forms that what use is the thermal laser recording mode with near-infrared～IR wavelength, exempt from the heat treatment plate as what adopt that this mode can form image, the crowd knows developable and phase-change type on ablative-type protective coating, the heat fused image layer machine.
On the other hand, as making the following printing plate material that has that the printing plate material that has exposure visible image on these printing plate materials of exempting from the processing type knows.
For example, have in the well-known image formation layer, contain colourless pigment and be called the layer that carries out the temperature-sensitive chromonic materials of its colour development material and so on or have the functional group's that produces sulfonic acid of being heated macromolecular compound and by the printing plate material (with reference to patent documentation 1,2) of the oleophilic layer of the compound of the acid generation variable color of generation.Have and contain the uveal printing plate material of IR-(with reference to patent documentation 3) that can utilize exposing of image formative element and its optical concentration can be changed, have that to contain the match peacefulness that optical concentration is changed by exposure be the printing plate material (with reference to patent documentation 4) of hydrophily protective finish more than the infrared ray absorbing pigment 20 quality %, that can remove on printing machine.
Yet, these printing plate materials since image formation layer etc. contain color development by exposure or fade, the pigment of variable color, so have when the exposure that utilizes laser etc. forms image, exist pigment might take place to distil or disperse, or be difficult to avoid the pollution that causes because of these pigments on machine, developing to printing ink, moistening water, to reach when developing on the machine and obtain normal printed article and many problems of paper loss amount sometimes.
In addition, in these the printing plate material, because being present in, the dispersion of materials of photo-thermal coversion material and color development or variable color constitutes in the layer, so in the time of will expecting sufficient exposure visible image, then development is insufficient on the sensitivity of printing plate material, the machine, is difficult to have concurrently printing adaptability and exposure visible image.
In addition, the known metal that produces owing to electrolytic coloring of in anodised pore, separating out, and with its printing plate material (patent documentation 5) that uses as the photo-thermal coversion material, but can not obtain exposure visible image.In addition, also know the photosensitive lithographic printing plate material (with reference to patent documentation 6) that uses dyestuff to make the aluminum support padding, this material can not obtain exposure visible image.
Patent documentation 1: the spy opens the 2000-225780 communique
Patent documentation 2: the spy opens the 2002-211150 communique
Patent documentation 3: the spy opens flat 11-240270 communique
Patent documentation 4: the spy opens the 2002-205466 communique
Patent documentation 5: the spy opens the 2000-267291 communique
Patent documentation 6: the spy opens flat 7-333831 communique
Summary of the invention
The object of the present invention is to provide in the printing of planographic printing plate material, but develop on the machine and give the exposure visible image formation method of testing edition planographic printing plate material of the printing process that property is good, colorrendering quality is good, pressrun is good.
Above-mentioned problem of the present invention is finished by following scheme.
The exposure visible image formation method of (scheme 1) planographic printing plate material, this method comprises, make planographic printing plate material carry out image exposure, and formation visual image, described planographic printing plate material comprises the image formation layer on aluminum support and the aluminum support, the surface of described aluminum support has the anodic oxidation coating pore, and wherein, described aluminum support has the coloured material that the generation look that is heated changes in its anodic oxidation coating pore.
The exposure visible image formation method of (scheme 2) scheme 1 described planographic printing plate material, wherein aforementioned aluminum support also have the photo-thermal coversion material in the anodic oxidation coating pore.
The exposure visible image formation method of (scheme 3) planographic printing plate material, it is characterized in that, in the exposure visible image formation method of scheme 2 described planographic printing plate materials, aforesaid anode oxide film thereon pore carries out sealing of hole after containing aforementioned coloured material and aforementioned lights thermal conversion material handles.
The exposure visible image formation method of any one described planographic printing plate material in (scheme 4) scheme 1～3, wherein aforementioned image formation layer are that heat sensitive image forms layer.
(scheme 5) a kind of aluminum support, it is used in the exposure visible image formation method of scheme 1～4 any one described planographic printing plate material.
(scheme 6) a kind of planographic printing plate material, it is used in the exposure visible image formation method of scheme 1～4 any one described planographic printing plate material.
The specific embodiment
The present invention is that the his-and-hers watches mask has the planographic printing plate material that has image formation layer on the aluminum support of anodic oxidation coating pore to carry out the exposure visible image method of formationing that image exposure forms the planographic printing plate material of visual image, it is characterized in that this aluminum support has to be heated to produce the coloured material of look variation in this anodic oxidation coating pore.
The present invention, especially by using that having in the anodic oxidation coating pore is heated and produce the aluminum support of the coloured material that look changes, can give that exposure visible image is good, to test edition property good and do not pollute printing-ink and colorrendering quality is good, pressrun is good printing process.
(aluminum support)
But the aluminum support that the present invention relates to cambial support that is load chart can use aluminium sheet.
Can use any in pure aluminum plate or the aluminium alloy plate as aluminium sheet.
Can use various aluminium alloys as aluminium alloy, for example, can use the metal of silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron etc. and the alloy of aluminium, can use the aluminium sheet that adopts various calendering process to make.
The aluminum support that the present invention relates to is a support of having implemented anodized, the anodic oxidation coating pore that produces when having anodized on its surface.
The present invention, having in this pore is heated produces the coloured material of change color.
Aluminum support preferably implements to remove the ungrease treatment that the surface of aluminum plate rolling oil is used, asperities processing before anodized.
As ungrease treatment, can adopt the ungrease treatment of the solvent that uses trichloro-ethylene, diluted material etc., use the emulsion ungrease treatment of emulsions such as kerosene (ケ シ ロ Application), three ethanol etc.
In addition, ungrease treatment also can be used the aqueous alkali of NaOH, potassium hydroxide, sodium carbonate, sodium phosphate etc.The occasion of aqueous alkali is used in ungrease treatment, also can remove and only adopt inexpungible dirt of above-mentioned ungrease treatment or oxide film thereon.
Use the occasion of aqueous alkali in the ungrease treatment, preferably be immersed in the acid of phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, chromic acid etc., or implement neutralisation treatment in these sour mixed acid.
Carry out the occasion of electrolysis asperitiesization after the neutralisation treatment, especially preferably the acid that will be used for neutralizing is added to the acid that is used for the electrolysis asperitiesization.
Preferably adopt the electrolysis asperities processing of known method as asperitiesization,, also can carry out the chemical asperitiesization of appropriate combination appropriateness treating capacity and the asperities processing of mechanical asperitiesization as this preliminary treatment.
The chemistry asperitiesization is similarly used aqueous alkalis such as NaOH, potassium hydroxide, sodium carbonate, sodium phosphate with ungrease treatment.
Preferably be immersed in the acid of phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, chromic acid etc. after the processing, or implement neutralisation treatment in these sour mixed acid.Carry out the occasion of electrolysis asperitiesization after the neutralisation treatment, especially preferably the acid that will be used for neutralizing is added to the acid that is used for the electrolysis asperitiesization.
The machinery asperitiesization does not have particular restriction, but preferably brushing, honing.
The base material of asperitiesization mechanically in order to remove the grinding-material that embeds substrate surface, aluminium bits etc., or the shape of control hole groove, preferably is immersed in the aqueous solution of acid or alkali etching is carried out on the surface.
As acid, for example sulfur acid, persulfuric acid, fluoric acid, phosphoric acid, nitric acid, hydrochloric acid etc.As alkali, for example, contain NaOH, potassium hydroxide, sodium carbonate, sodium phosphate etc.Wherein, preferably use the aqueous solution of alkali.
Mechanically use the thin grinding-material of fineness ratio #400 in the asperities processing, and carry out etch processes in asperities processing part mechanically by using aqueous alkali, can make that complicated asperities structure becomes smooth concavo-convex surface due to the mechanically asperities processing.
The aqueous solution that uses alkali preferably is immersed in the acid of phosphoric acid, nitric acid, sulfuric acid, chromic acid etc., or implements neutralisation treatment in these sour mixed acid above-mentioned occasion of carrying out impregnation process.
The occasion of carrying out the processing of electrolysis asperities after the neutralisation treatment, preferably the acid that neutralization is used is added in the acid of electrolysis asperities processing use.
The processing of electrolysis asperities generally is to use alternating current to carry out the processing of asperitiesization in acidic electrolysis bath.The acidic electrolysis bath that acidic electrolysis bath can use common electrolysis asperities method to use is an electrolyte but preferably use hydrochloric acid system or nitric acid, and it is electrolyte that the present invention especially preferably uses hydrochloric acid.
The power supply wave shape that electrolysis is used can use various waveforms such as square wave, trapezoidal wave, saw shape ripple, but preferred especially sinusoidal wave.
In addition, also can preferably use and open as the spy that flat 10-869 communique is disclosed cuts apart the processing of electrolysis asperities.
Preferred 1～the 50V of voltage that applies when using the electrolysis asperities of nitrose electrolyte, more preferably 5～30V.
Preferred 10～the 200A/dm of current density (peak value) 2, more preferably 20～150A/dm 2
All the power consumption of treatment process total is 100～2000C/dm 2, preferred 200～1500C/dm 2, more preferably 200～1000C/dm 2
Preferred 10～50 ℃ of temperature, more preferably 15～45 ℃.Concentration of nitric acid 0.1～5 quality %.
Can add nitrate, chloride, amine, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid etc. as required in the electrolyte.
The aluminum support of electrolysis asperities processing among the present invention in order to remove the dirt etc. on surface, or in order to control hole groove shape etc., is immersed in the etching of carrying out the surface in the aqueous solution of alkali.
As aqueous alkali, contain NaOH, potassium hydroxide, sodium carbonate, sodium phosphate etc.
Preferably using aqueous alkali to carry out etch processes aspect printing (brushing out property) or the scumming.
After in the aqueous solution of alkali, carrying out impregnation process, preferably be immersed in phosphoric acid, nitric acid, sulfuric acid, chromic acid etc. acid or these sour mixed acid in implement neutralisation treatment.Carry out the occasion of anodized after the neutralisation treatment, the acid of using that especially preferably will neutralize is added in the acid of anodized use.
Aluminum support is implemented anodized after the asperities processing.
The method of the anodized of using among the present invention does not have particular restriction, can adopt known method.
On base material, form punctulate anodic oxidation coating by anodized.Or become aluminium oxide by anodized aluminium and form alumina coating, in the growth course of this oxide film thereon, form the tunicle of porous.Moreover the aperture of these pores is
Figure C20068000327600071
Among the present invention, anodized, preferably the aqueous solution with 10～50% concentration sulfur acid and/or phosphoric acid etc. is electrolyte.At current density 1～10A/dm 2Carry out the method for electrolysis under the condition, in addition, also can adopt United States Patent (USP) the 1st, 412, No. 768 described methods of in sulfuric acid, carrying out electrolysis under the high current density, or the 3rd, 511, No. 661 described use phosphoric acid of United States Patent (USP) carry out the method for electrolysis etc.
The coloured material that the so-called thermocolour that the present invention relates to changes, the material of change color takes place in the heat that produces when being meant owing to exposure, and so-called change color is meant that maximum absorption wavelength (λ max) changes, or the absorbance of λ max changes.
The former variation mainly is the variation of following form and aspect or chroma, and the latter mainly is the variation of following brightness.The advantageous variant amount of λ max is according to the color of coloured material before changing or concentration and difference, preferred 20nm～300nm, and the advantageous variant amount of the absorbance of λ max is 5%～95%.
Can use the dyestuff of the painted use of anodic oxidation coating etc. as coloured material, for example, can enumerate trade name TAC YELLOW-SLH, TAC YELLOW-RBL, TAC YELLOW-RHM, De Star プ シ ユ ウ テ Star ア Application, TAC ORANGE-SLH, TAC ORANGE-LH, TACORANGE-CH, TAC ORANGE-TCH, TAC RED-GD, TAC FIERYRED-GBM, TAC RED-SCH, TAC RED-BLH, TAC VIOLET-SLH, TAC SKYBLUE-GLH, TAC BLUE-SLH, TAC BLUE-RCD, TAC GREEN-GM, TAC GREEN-SBM, TAC BRONZE-GM, TAC BROWN-GR, TAC BROWN-GR, TAC BROWN-RH, TAC BLACK-GLH, TAC BLACK-GRLH, TAC BLACK-SG, TACBLACK-LSH, TAC BLACK-GBLH, TAC BLACK-GNB, TAC BLACK-NBLH, TAC BLACK-BLH, ト Star プ ADD-500 (the wild pharmaceuticals industry corporate system of above Austria) etc.
Make and contain coloured material in the pore, can be immersed in by the aluminum support with anodized dyes to make in the anodic oxidation coating pore in the bath that contains the coloured material that makes coloured material dissolving, dispersion etc. contains coloured material.
The content that preferably contains the coloured material in the bath of coloured material dyes in the scope of 0.1～10g/L, and in addition, the pH of preferred this bath dyes in 4.0～7.0 scope.
Before carrying out above-mentioned dyeing, preferably aluminum support is washed fully, so that remove dissolved aluminum, dissolve sulfur acid group etc.
Anodized and have coloured material aluminum support, can also implement sealing of hole as required and handle.
These sealing of holes are handled and can be adopted known method such as hot water treatment, boiled water processing, steam treatment, the processing of the bichromate aqueous solution, nitrite treatments, ammonium acetate processing to carry out.
In addition, the base material of anodized also can carry out above-mentioned sealing of hole processing surface treatment in addition aptly.
As surface treatment, can enumerate the known processing of silicate processing, phosphate treated, the processing of various organic acid, PVPA processing, boehmite processing and so on.In addition, also can adopt the spy to open the processing that flat 8-314157 number the described aqueous solution that contains bicarbonate carries out, or adopt after the processing of the aqueous solution that contains bicarbonate, then carry out handling as the organic acid of citric acid and so on.
So long as can be installed in and then do not have particular restriction on the printing machine, the thickness of general 50～500 μ m is operation easily then as the thickness of aluminum support.
(photo-thermal coversion material)
The present invention considers from visual image, colorrendering quality aspect, also contains the photo-thermal coversion material in the preferred anodes oxide film thereon pore.
This estimate because coloured material be present in the photo-thermal coversion material near, then the efficient of the change color of coloured material improves, and more owing to coloured material is fixed on the pollution that prevents in the pore printing-ink etc.
The photo-thermal coversion material is the material that can produce heat by image exposure, for example can enumerate INFRARED ABSORPTION pigment, pigment etc.
As the INFRARED ABSORPTION pigment, can enumerate, for example, be that pigment, chromium (Network ロ コ ニ ウ system) are that pigment, polymethine are that pigment, Azulene are that pigment, spiny dogfish system (ス Network ワ リ ウ system) pigment, sulfo-pyrans are that pigment, naphthoquinones are that pigment, anthraquinone are organic compound, phthalocyanine system, naphthalene cyanines system, azo system, thioamides system, the two mercaptan system of pigment etc., the metal-organic complex of indoaniline system etc. as the match peacefulness of general INFRARED ABSORPTION pigment.
As pigment, can enumerate carbon, graphite, metal, metallic compound etc.
Make and contain the photo-thermal coversion material in the pore, can be undertaken by being immersed in to make it in the solution that contains the photo-thermal coversion material to adsorb.
Among the present invention, as the photo-thermal coversion material, from colorrendering quality, the visual image aspect is considered, the preferred compound that uses metal or contain metal particularly preferably is by carry out metal or the metallic compound that electrolytic treatments generates in the anodic oxidation pore in containing the electrolyte of metal ion.
As electrolytic treatments, can enumerate, for example, the antianode oxide film thereon is carried out the method for alternating current electrolysis in the electrolyte of the slaine that contains Ni, Cu, Se, Sn etc., carries out method of dc electrolysis anode oxide film etc. in the electrolyte of the slaine of Ni etc.
Use the occasion of the photo-thermal coversion material that this electrolytic treatments generates, preferably carry out, carry out occasion that above-mentioned sealing of hole handles and preferably handle after this carrying out sealing of hole again according to this electrolytic treatments, the order that contains the processing of above-mentioned coloured material.
Promptly, the preferred mode of exposure visible image formation method of planographic printing plate material, it is characterized in that in the exposure visible image formation method of aforementioned schemes 2 described planographic printing plate materials aforesaid anode oxide film thereon pore carries out the sealing of hole processing after containing aforementioned coloured material and aforementioned lights thermal conversion material.
(image formation layer that can develop on the machine)
The image formation layer that the present invention relates to is the layer that can form image by image exposure, the occasion of the image formation layer that can develop on the special preferably machine.
The image formation layer that can develop on the so-called machine, be meant behind the image exposure especially without developing procedure and become the image formation layer of the part of non-image portion in the moment of supplying with to printing process, when promptly utilizing moistening water or moistening water and printing-ink to remove to print in the printing preparatory stage, can form the image formation layer of printable image, wherein big especially as the cambial occasion of heat sensitive image effect of the present invention.
Heat sensitive image forms layer, is to form layer by containing the heat sensitive image that heat release that light with image exposure converts the photo-thermal coversion material layer of heat to can form image.
The layer that contains the photo-thermal coversion material can be the image formation layer that the present invention relates to, and also can be hydrophilic layer, or forms other layer of layer adjacency with heat sensitive image.
Form layer as heat sensitive image, especially preferably use the image formation layer of exposure portion to be heated towards the so-called minus image formation layer that is fixed on the direction variation on the hydrophilic layer.
As the image formation layer that above-mentioned exposure portion is heated and changes towards the direction that is fixed on the hydrophilic layer, can enumerate, for example, containing before the exposure is hydrophilic layer, the image formation layer of the hydrophobization precursor that can be changed to hydrophobic layer by hydrophilic layer of being heated.
As the hydrophobization precursor, can enumerate the thermoplasticity hydrophobic particles of hot melt property particle or hot-melt-bondable particle etc., the microcapsules of interior bag lyophobic dust.Blocked isocyanate compounds, the polymer that for example is heated and changes to hydrophobicity by hydrophily (water-soluble or water-swellable), particularly for example, the spy opens the disclosed polymer that contains aryl diazosulfonate unit of 2000-56449.
As above-mentioned thermoplasticity hydrophobic particles, can enumerate hot melt property particle described later and hot-melt-bondable particle.
So-called hot melt property particle is that the viscosity during fusion is low especially in the thermoplastic, generally the particle that forms with the material as the wax classification.As rerum natura, preferred softening point is 40 ℃～120 ℃, 60 ℃～150 ℃ of fusing points, and more preferably softening point is 40 ℃～100 ℃, 60 ℃～120 ℃ of fusing points.Keeping quality was a problem when fusing point was lower than 60 ℃, and the sticking wall sensitivity of the occasion printing ink of fusing point than 300 ℃ high reduces.
As spendable material, can enumerate paraffin, polyolefin, Tissuemat E, microwax, fatty acid series wax etc.These are the wax of molecular weight 800～10000.Perhaps, for easy emulsification also can be with these wax oxidations, and introduce hydroxyl, ester group, carboxyl, aldehyde radical, peroxy isopolarity base.In addition, in order to reduce softening point or to improve operation also can be added stearmide, flax acid amides, lauramide, myristamide, curing beef fat acid acid amides, lemon palmitic acid acid amides, oleamide, rice sugar fatty acid acid amides, coconut fatty acid acid amides or these fatty acid amides in these wax hydroxymethylate, di-2-ethylhexylphosphine oxide stearmide, ethylenebisstearamide etc.Perhaps, also can use the copolymer of coumarone-indene resin, rosin modified phenolic resin, terpene modified phenolic resins, xylene resin, ketone resin, acrylic resin, iolon and these resins.
Wherein, preferably contain any in polyethylene, crystallite, fatty acid ester, the aliphatic acid.These material forms so can carry out highly sensitive image because fusing point is lower, and melt viscosity is also low.
As the hot-melt-bondable particle, can enumerate thermoplasticity hydrophobic polymer polymer particle, the softening temperature of high molecular polymer particle is not had specific upper limit, but preferred temperature is lower than the decomposition temperature of high molecular polymer particle.The weight average molecular weight (Mw) of preferred high molecular polymer is 10,000～1,000,000 scope.
As the concrete example of the high molecular polymer that constitutes the high molecular polymer particle, for example, can enumerate diene (being total to) polymer class of polypropylene, polybutadiene, polyisoprene, ethylene-butadiene copolymer etc.The synthetic rubber class of SB, methyl methacrylate butadi ene copolymer, acrylonitrile-butadiene copolymer etc.Vinyl esters (being total to) polymers of (methyl) acrylate of polymethyl methacrylate, methyl methacrylate-(2-EHA) copolymer, methyl methacrylate-methacrylic acid copolymer, methyl acrylate-(N hydroxymethyl acrylamide) copolymer, polyacrylonitrile etc., (methyl) acrylic acid (being total to) polymers, polyvinyl acetate, vinyl acetate-vinyl propionate copolymer, vinyl acetate-ethylene copolymer etc.Vinyl acetate-(2-EHA) copolymer, polyvinyl chloride, Vingon, polystyrene etc. and these copolymer.Wherein, preferred (methyl) acrylate, (methyl) acrylic acid (being total to) polymer, vinyl esters (being total to) polymer, polystyrene, synthetic rubber class.
[end-blocking isocyanate compound]
Blocked isocyanate compounds is to make the end-capping reagent of following record and the compound of isocyanate compound reaction addition.
The spendable blocked isocyanate compounds water dispersion of compound as described later preferably in the image formation layer.
Form by being coated with, can obtain development property on the good machine by water dispersion.
[isocyanate compound]
As isocyanate compound, can enumerate aromatic polyisocyanate [methyl diphenylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), polyphenyl polymethylene polyisocyanates (rough MDI), naphthalene diisocyanate (NDI) etc.]; Aliphatic polyisocyante [1,6-hexamethylene diisocyanate (HDI), LDI (LDI) etc.]; Ester ring type polyisocyanates (IPDI (IPDI)), dicyclohexyl methyl hydride diisocyanate (hydrogenation MDI), cyclohexalene vulcabond etc.]; Aromatic-aliphatic polyisocyanates [XDI (XDI), tetramethyl xylylene diisocyanate (TMXDI) etc.]; These modifier (containing biuret groups, isocyanuric acid ester group, carbodiimide-based, oxazole alkyl modifier etc.); The carbamate prepolymer that compound bearing active hydrogen constitutes that contains with these polyisocyanates and molecular weight 50～5,000 with isocyanate end.
[end-capping reagent]
End-capping reagent as NCO can use known end-capping reagent.For example, the alcohol that can enumerate methyl alcohol, ethanol etc. is end-capping reagent, and phenol such as phenol, cresols are end-capping reagent, and the oxime of formaldoxime, acetaldoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, acetoxime, diacetyl monoxime, diphenyl-ketoxime etc. is an end-capping reagent.Sour acid amides such as acetanil, epsilon-caprolactams, butyrolactam are end-capping reagent, dimethyl malenate, methyl acetoacetate isoreactivity methylene base system end-capping reagent, mercaptan such as butyl mercaptan are imide series end-capping reagents such as end-capping reagent, succinimide, maleimide, imidazoles such as imidazoles, glyoxal ethyline is an end-capping reagent, urea such as urea, thiocarbamide is an end-capping reagent, carbamic acids such as N-phenylcarbamic acid phenyl ester are end-capping reagent, amine such as diphenylamines, aniline is end-capping reagent, and second is embraced imines, poly-second, and to embrace imines such as imines be end-capping reagent etc.Wherein, especially preferably using oxime is end-capping reagent.
Image formation layer can contain water-soluble material, can enumerate material described as follows as water-soluble material.
[water-soluble high-molecular compound]
As the water-soluble material that contains in the image formation layer, can enumerate the known water-soluble high-molecular compound in the aqueous solution that is dissolved in pH4～pH10.
Can enumerate resins such as polysaccharide, PEO, PPOX, polyvinyl alcohol, polyethylene glycol (PEG), polyvingl ether, polyacrylic acid, polyacrylate, polyacrylamide, PVP particularly.
Wherein, preferred polysaccharide class, polyacrylic acid, polyacrylate, polyacrylamide, PVP.
As polysaccharide, can use starch based, cellulose family, polyuronide, pullulan, shitosan, or these derivative etc., especially the fiber derivative of preferable methyl cellulosate, carboxymethyl cellulose salt, hydroxyethylcellulose salt etc., the more preferably sodium salt of carboxymethyl cellulose or ammonium salt.
As polyacrylic acid, polyacrylate, polyacrylamide, preferred molecular weight is 3000～1,000,000, is more preferably 5000～500,000.
Wherein, this polyacrylate of Sodium Polyacrylate most preferably.Polyacrylate can improve the hydrophily on the surface of the hydrophilic layer that presents as the effect height of the hydrophilicity-imparting treatment material of hydrophilic layer after developing on the image formation layer machine.
[compound sugar]
As water-soluble material, except above-mentioned water-soluble high-molecular compound, can also contain compound sugar.
As compound sugar, can enumerate the compound sugar of gossypose, trehalose, maltose, galactolipin, sucrose, lactose and so on, but preferred especially trehalose.
[materials of other that can contain in the image formation layer]
In addition, can also contain image formation layer in the image formation layer, can use and the same material of aforesaid photo-thermal coversion material as material with light thermal conversion material.
For example, contain the occasion of infrared ray absorbing pigment, as its content, must be according to the coloring degree of pigment under visible light, and be necessary to consider with machine on the taking into account of printing machine dirt when developing, but on general per unit area as printing plate material, 0.001g/m preferably 2More than, but be lower than 0.2g/m 2, more preferably be lower than 0.05g/m 2
In addition, with light thermal conversion material,, can preferably use following material as image formation layer as spendable metal, metallic compound.
As metal, so long as particle diameter is below the 0.5 μ m, below the preferred 100nm, more preferably the following particulate of 50nm then can use any metal.As shape can be spherical, sheet, the shape that needle-like etc. are any.Preferred especially colloid shape metal particle (Ag, Au) etc.
As metal oxide, can use the material that is black at visible domain, or material itself there is electric conductivity, or the material of semiconductor and so on.
As the former, can enumerate black iron oxide (Fe 3O 4) or contain the black composite metal oxide of the metal more than two kinds.
As the latter, for example can enumerate the SnO of doping Sb 2(ATO), add the In of Sn 2O 3(ITO), TiO 2, with TiO 2The TiO that has reduced (titanium oxynitrides usually is that titanium is black) etc.
In addition, also can use and utilize these metal oxides lining core (BaSO 4, TiO 2, 9Al 2O 32B 2O, K 2OnTiO 2Deng) material.
The particle diameter of these materials is below the 0.5 μ m, below the preferred 100nm, more preferably below the 50nm.
In these photo-thermal coversion materials, can enumerate contain metal more than two kinds the black composite metal oxide as preferred material.
Comprise the composite metal oxide of metal more than two kinds that is selected among Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, the Ba specifically.These composite metal oxides can adopt the spy to open flat 8-27393 communique, spy and open flat 9-25126 communique, spy and open that flat 9-237570 communique, spy are opened flat 9-241529 communique, the spy opens disclosed method manufacturings such as flat 10-231441 communique.As the composite metal oxide that the present invention uses, particularly preferably be the composite metal oxide of Cu-Cr-Mn system or Cu-Fe-Mn system.The occasion of Cu-Cr-Mn system for the stripping that makes 6 valency chromium reduces, is preferably implemented the spy and is opened the disclosed processing of flat 8-27393 communique.These composite metal oxide is painted to addition, that is, the photo-thermal conversion efficiency is good.
The average grain diameter of preferred 1 particle of these composite metal oxide is that more preferably the average grain diameter of 1 particle is in the scope of 0.01～0.5 μ m below the 1 μ m.Average grain diameter by 1 particle becomes below the 1 μ m, and then the photo-thermal conversion to addition can become better, becomes the scope of 0.01～0.5 μ m by the average grain diameter of 1 particle, and then the photo-thermal conversion to addition can become better.
Yet the photo-thermal conversion of addition can be influenced by the dispersion of nano-particles degree also greatly relatively, and the photo-thermal conversion can be better better for decentralization.
Therefore, these composite metal oxide particles, in the coating fluid that adds layer to before, preferably adopt other known method to disperse, form dispersion liquid (paste).The average grain diameter of 1 particle is less than 0.01 o'clock, difficulties in dispersion, so not preferred.Dispersion can be used suitable dispersant.The addition of dispersant is with respect to preferred 0.01～5 quality % of composite metal oxide particle, more preferably 0.1～2 quality %.
In addition, can contain surfactant in the image formation layer.Can make Si system, or the surfactant of F system etc., the preferred especially surfactant that contains the Si element that uses, the printing of not worrying producing is polluted.The content preferred hydrophilic layer of this surfactant is 0.01～3 quality %, more preferably 0.03～1 quality % of (as the solid constituent of coating fluid) all.
(protective layer)
On image formation layer, protective layer can be set.As the material that uses in the protective layer, can preferably use water-soluble resin, water-dispersed resin.
In addition, also can preferably use the spy to open 2002-019318 number or the spy drives described hydrophily protective finish 2002-086948 number.
Adhesion amount as protective layer is 0.01～10g/m 2, 0.1～3g/m preferably 2, 0.2～2g/m preferably again 2
(image exposure)
The image exposure that the present invention relates to is by carrying out from the surface irradiation laser that planographic printing plate material has image formation layer according to view data.
More specifically preferred the use infrared and/or near infrared region is luminous among the present invention, promptly the wave-length coverage of 700～1500nm is carried out the scan exposure of luminous laser instrument.
As laser instrument, can the using gases laser instrument.But preferred especially the use carried out luminous semiconductor laser near infrared region, carries out scan exposure.
As the device that the spendable scan exposure of the present invention is suitable for, can then can the device of any way at the device of printing plate material image forming surface according to picture signal from computer so long as use semiconductor laser.
Usually, can enumerate the laser beam that (1) uses 1 or many and carry out the mode that the scanning of two dimension exposes printing plate material comprehensively remaining on printing plate material on the tabular maintaining body, (2) use is from 1 or many laser beam of cylinder interior, inboard at fixing maintaining body cylindraceous, Zhou Fangxiang (main scanning direction) for the printing plate material edge cylinder that keeps along barrel surface scans, the limit makes it to move the mode that printing plate material is exposed comprehensively along the direction vertical with Zhou Fangxiang (sub scanning direction), (3) use is from 1 or many laser beam of cylindrical outer, printing plate material on the cylindric drum surface that the axle that remains on as rotary body is rotated for the center scans by the rotation edge Zhou Fangxiang (main scanning direction) of rotating cylinder, the limit makes it to move the mode that printing plate material is exposed comprehensively along the direction vertical with Zhou Fangxiang (sub scanning direction).
Planographic printing plate material behind the image exposure is delivered to as required and is tested an edition operation.
Then, for example especially do not need the occasion of the planographic printing plate material of development treatment, deliver to printing process.
This occasion, non-image (unexposed portion) of the image formation layer on the printing machine removes, can the limit rotation version body limit make it the contact zones damping roller or ink roller carries out, but also can according to as the following example of enumerating, or various order is in addition carried out.In addition, also can increase the water yield with respect to the needed wet water water yield of when printing this moment, or reduce and carry out the water yield and regulate, and also can regulate the water yield be divided into the multistage, or make it to change continuously and carry out.
(1) order as the printing beginning is to make it the contact zones damping roller, makes edition body rotation 1 circle～tens of circles, contacts ink roller then and makes edition body rotation 1 circle～tens of circles, then begins printing.
(2) order as the printing beginning is to make it to contact ink roller to make edition body rotation 1 circle～tens of circles, and the contact zones damping roller makes edition body rotation 1 circle～tens of circles then, then begins printing.
(3) as the order of printing beginning, be in fact side by side to make it contact zones damping roller and ink roller, make edition body rotation 1 circle～tens of circles, then begin printing.
Embodiment
Below, specifically describe the present invention by embodiment, still, the present invention is not limited to these embodiment.In addition, " part " among the embodiment is not if illustrate especially then expression " mass parts ".
Embodiment 1
[manufacturing of base material]
The aluminium sheet of thickness 0.24mm (material 1050, modified H16) is immersed in 50 ℃ the 1 quality % sodium hydrate aqueous solution, carrying out dissolution process, to make meltage be 2g/m 2, after washing, in 25 ℃ 0.1 quality % aqueous hydrochloric acid solution, flooded for 30 seconds.Wash after the neutralisation treatment.
Then, use the electrolyte that contains hydrochloric acid 10g/L, aluminium 0.5g/L, utilize sinusoidal wave interchange, at peak current density 50A/dm 2Condition under this aluminium sheet is carried out the processing of electrolysis asperities.
The electrode of this moment and the distance of specimen surface are 10mm.The processing of electrolysis asperities is divided into 12 times and carries out.Making each processing electric weight (during anode) is 40C/dm 2Add up to 480C/dm 2Processing electric weight (during anode).And, stop time in 5 seconds is set between the asperities processing of each time.
After the electrolysis asperitiesization, be impregnated in the 1 quality % sodium hydrate aqueous solution that remains on 50 ℃ and carry out etching, the meltage that makes the face of asperitiesization contain dirt is 1.2g/m 2, wash, then dipping was washed after the neutralisation treatment after 10 seconds in remaining on 25 ℃ 10% aqueous sulfuric acid.Then, in 20% aqueous sulfuric acid, carrying out anodized under the rated voltage condition of 20V, to make electric weight be 150C/dm 2, wash again.
Then, squeeze out the surface water after the washing after, wash the back 80 ℃ of dryings 5 minutes 30 seconds of dipping in remaining on 70 ℃ the biphosphate sodium water solution of 1 quality %, make base material 1.
The Ra of base material 1 is 460nm (uses WYKO corporate system RST Plus, measure by 40 times).
[giving of the photo-thermal coversion material in the antianode oxide film thereon pore]
Use base material 1 to adopt electrocolor process, in the pore of anodic oxidation coating, in containing the electrolyte of metal ion, adopt the constant voltage method that exchanges to carry out handling in 1 minute 30 seconds precipitating metal particulate in the pore that makes in the anodic oxidation.
As the electrolyte that contains metal ion, use stannous sulfate, under following electrolytic condition, carry out painted.
Electrolyte: stannous sulfate 10g/L, sulfuric acid 10g/L, catechol 5g/L.
31 ℃ of treatment temperatures, voltage 15V, the soft start of 15 seconds accent machines.
[giving of the coloured material in the antianode oxide film thereon pore]
Then, use sodium acetate and acetic acid that the 7.5g/L aqueous solution of the wild pharmaceuticals industry system TACRED-SCH of Co., Ltd difficult to understand (red 106) is adjusted to pH5.0, in the bath of 55 ℃ of insulations, while stirring base material was flooded 10 minutes, carry out anodic oxidation coating painted.
[sealing of hole processing]
After the aqueous solution of following composition is adjusted to pH5.5, be heated to 85 ℃, while stirring above-mentioned painted base material dipping carried out sealing of hole in 15 minutes and handle.
Nickel acetate 5g/L
Cobalt acetate 1g/L
Boric acid 8g/L
The reflection density on the aluminium base surface after sealing of hole is handled is 1.8.GretagMacbeth corporate system beam split densimeter Spectrolino is used in concentration determination, according at filter condition D65, and 2 ° in the observation visual field, Bai Ji: absolute white, the reflection density of the pH-value determination pH that concentration standard: Status-T measures down black (K).
Then, make carboxymethyl cellulose 1150 (Daicel chemistry Co., Ltd system) become the aqueous solution of solid component concentration 0.1 quality %, in the liquid temperature remains on 75 ℃ bath, flooded for 30 seconds while stirring after, drying is carried out in washing.
[manufacturing of planographic printing plate material]
[printing plate material 1]
After the material of following composition mixed fully, suitably dilute adjusting concentration, filter, obtain the coating fluid that the following image formation layer (1) of solid constituent 2.5 quality % is formed with pure water.
Then, use to step steel wire bar is coated with image formation layer (1) on base material coating fluid, regulate dried adhesion amount and make it to become 0.4g/m 2, following dry 3 minutes 50 ℃ of temperature.
Then, carry out 40 ℃ of etch processes of 24 hours, make printing plate material 1.
Mass parts is than the quality ratio in the dried solid constituent of expression.
Image formation layer (1) coating fluid is formed
Temperature-sensitive material: 155 parts of end-sealed type carbamate prepolymer aqueous dispersions (the military field of Mitsui chemistry Co., Ltd system, Network ネ one ト WB-700 solid constituent 44 quality %)
Water-soluble resin: Sodium Polyacrylate, the aqueous solution of ア Network ア リ Star Network DL 522 (Japanese catalyst corporate systems), 40 parts of solid constituent 10 quality %
800 parts of the 1 quality % aqueous solution of INFRARED ABSORPTION pigment: ADS830WS (American DyeSource corporate system)
400 parts of 5% aqueous solution of system hydrophily montmorillonite (the ス メ Network イ ト) SWN of layer mineral particle: コ one プ ケ ミ カ Le Co., Ltd
[adopting the image of infrared laser exposure to form]
The printing plate material coiling is fixed on the exposure rotating cylinder.Use laser beam, the exposure energy of wavelength 830nm, the about 18 μ m in luminous point footpath to be 400mJ/cm in the exposure 2,, use 175 line formed images by 2400dpi (so-called dpi represents counting of every 2.54cm).The image of exposure is the halftone dot image that contains image on the spot and 1～99%.
[printing process]
Printing machine: use the system DAIYAIF-1 of Mitsubishi Heavy Industries, coated paper, wet water: ア ス ト ロ マ one Network 3 (day is ground the chemistry institute corporate system) 2 quality %, printing ink (Toyo Ink corporate system TK Ha イ ユ ニ テ イ is red) prints.Printing plate material exposure back is installed on edition body under its original state, uses with the same print order of PS version and prints.The concentration adjustment of the portion of image on the spot of printed article became for 1.4 (the concentration determination condition as hereinbefore).
(evaluation)
[color turbidity]
Use printing machine that printing plate material is carried out 100 printing treatment, use GretagMacbeth corporate system beam split densimeter Spectrolino, mensuration is from being printed onto the L*a*b* value of non-image portion of the 10th printing, obtain aberration (Δ E) with the L*a*b* value of printing preceding printing, the evaluate color turbidity is the index of this aberration as colorrendering quality.In the practicality so long as 0.6 with next be no problem level.
The printing of printing plate material finishes back cleaning printing machine, carries out the printing-ink to new printing product, the replacing of wet water.
[evaluation of visual image]
Printing plate material after the image that adopts the infrared laser exposure formed is observed under the light source of グ レ グ マ Network ベ ス corporate system, standard sources device プ Le one Off ラ イ ト (reflection with) LD 50-440 type, observes the image of site step (ス テ Star プ) portion.
To could comparing of the identification of the different step grey jump (Bands Tone is poor) each other of site % this moment.
Evaluation criterion
5: whole regional site GTG difference % that can visual differentiation site 1%～99% is the poor of 5% step.
4: the grey jump of regional site that can visual differentiation site 5%～95% is the poor of 5% step.
3: the grey jump of regional site that can visual differentiation site 10%～90% is the poor of 20% step.
2: step that can visual differentiation site 0% (unexposed portion) and 50% and 100% (portion of exposure on the spot) poor.
1: step that can visual differentiation site 0% (unexposed portion) and 100% (portion of exposure on the spot) poor.
[anti-seal]
To each printing plate material, from brush out 20000 printing, whether the defective of inadhesive small printing ink takes place, the results are shown in table 1 when using 20 times of amplifying lens visualization 3% site portions when observing the printing of opening arbitrarily.
Embodiment 2
Sealing of hole in the manufacturing process that saves printing plate material 1 similarly makes printing plate material 2 handling.
The evaluation of using printing plate material 2 to carry out similarly to Example 1.The results are shown in table 1.
Embodiment 3
Photo-thermal coversion material in the manufacturing process that saves printing plate material 1 in the antianode oxide film thereon pore is given the operation, similarly makes printing plate material 3.The results are shown in table 1.
Embodiment 4
Sealing of hole in the manufacturing process that saves printing plate material 1 is handled and the photo-thermal coversion material in the anode oxidation tunicle pore is given the operation, similarly makes printing plate material 4.The results are shown in table 1.
Comparative example 1
Sealing of hole processing in the manufacturing process that saves printing plate material 1 is given the operation with the coloured material in the antianode oxide film thereon pore, similarly makes printing plate material 5.
Comparative example 2
Sealing of hole in the manufacturing process that saves printing plate material 1 handle with antianode oxide film thereon pore in the photo-thermal coversion material give with coloured material and giving the operation, similarly make printing plate material 6.
But develop on the image forming method machine of the present invention as seen from Table 1, it is good and to test edition property good to give exposure visible image, and does not pollute printing-ink and colorrendering quality is good, the printing process that pressrun is good.
[table 1]
Industrial applicibility
According to such scheme of the present invention, develop on the machine but can provide in the printing of planographic printing plate material, It is good and test an edition property excellence to give exposure visible image, and do not pollute printing-ink and color again Existing property excellence, the exposure visible image side of formation of the planographic printing plate material of the printing process that anti-seal is good Method.

Claims (6)

1. the exposure visible image formation method of a planographic printing plate material, this method comprises, make planographic printing plate material carry out image exposure, and formation visual image, described planographic printing plate material comprises the image formation layer on aluminum support and the aluminum support, the surface of described aluminum support has the anodic oxidation coating pore, wherein, described aluminum support has the coloured material of the generation change color of being heated in its anodic oxidation coating pore, the coloured material of change color takes place in described being heated, it is the material that change color takes place owing to the heat that when exposure produces, described change color is meant maximum absorption wavelength, be that λ max changes, or the absorbance of λ max change.
2. the exposure visible image formation method of the described planographic printing plate material of claim 1, wherein, described aluminum support also has the photo-thermal coversion material in the anodic oxidation coating pore.
3. the exposure visible image formation method of the described planographic printing plate material of claim 2, wherein, described anodic oxidation coating pore carries out sealing of hole after containing aforementioned coloured material and aforementioned lights thermal conversion material handles.
4. the exposure visible image formation method of any one described planographic printing plate material in the claim 1～3, wherein, described image formation layer is that heat sensitive image forms layer.
5. aluminum support, it is used for the exposure visible image formation method of any one described planographic printing plate material of claim 1～4.
6. planographic printing plate material, it is used for the exposure visible image formation method of any one described planographic printing plate material of claim 1～4.
CNB2006800032769A 2005-01-31 2006-01-13 Exposure visible image formation method, aluminum support and the planographic printing plate material of planographic printing plate material Expired - Fee Related CN100551716C (en)

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