CN1221863C - Thermal sensitive lithographic printing front body - Google Patents

Thermal sensitive lithographic printing front body Download PDF

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CN1221863C
CN1221863C CN 00137019 CN00137019A CN1221863C CN 1221863 C CN1221863 C CN 1221863C CN 00137019 CN00137019 CN 00137019 CN 00137019 A CN00137019 A CN 00137019A CN 1221863 C CN1221863 C CN 1221863C
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lithographic printing
front body
thermal sensitive
sensitive lithographic
printing front
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CN1354394A (en
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喜多信行
秋山慶侍
大橋秀和
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Fujifilm Corp
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Fujifilm Corp
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Abstract

The present invention provides a precursor of a thermal sensitive lithographic printing plate, which comprises a hydrophilic layer on a substrate with a printing ink accepting surface or a substrate coated with a printing ink accepting layer. The precursor of the printing plate also has a water soluble outer coating on the hydrophilic layer. Besides, the hydrophilic layer is a three-dimensional crosslinking hydrophilic layer, and the heating region can be easily removed by plate dampening liquid or printing ink in the printing operation.

Description

Thermal sensitive lithographic printing front body
Technical field
The present invention relates to a kind of thermal sensitive lithographic printing front body, it can not need carry out development treatment and directly makes a plate, and can guarantee that the offset printing forme printing life-span is long.More particularly, the present invention relates to a kind of lithographic plate presoma, its image is noted by the digital signal scan exposure, and it can install on the printing machine after recording picture, and need be through just not carrying out presswork to the image development that is write down with traditional liquid developer.
Background technology
Usually, lithographic printing-plate is to be made up of the oleophylic image region of accepting printing ink in print steps and the hydrophilic non-image region of accepting fountain solution before last China ink there.Make a kind of like this lithographic printing-plate, comprise wet (being hydrophilic) support of water and the presensitized plate of accepting the photopolymer layer of printing ink (being called for short " PS " version afterwards), be widely used as plate.In the classic method that adopts the required forme of this PS version system, usually by a kind of initial exposing as the lithographic plate film mode, but not image region is by developer dissolves and removal.
In conventional process, require after exposure, to remove the step of non-image region by dissolving with PS version seal carving version.The improvement desired to conventional art, target are not need or simplify this additional wet process.Particularly recent, as to discharge in procedure for wet processing liquid waste processing from the viewpoint of global environment, has become the major issue that involves whole world industry.Therefore, become more important from the desired improvement in this aspect.
Propose a kind of simple method for platemaking at its requirement, be included in the common printing treatment process, utilized the picture record layer, can remove the non-image region of plate presoma like this, and after exposure, can on printing machine, develop, thereby obtain last forme.The system for preparing lithographic printing-plate according to the method described above is meant " developing at seal " system.Therefore its concrete example, what can mention is, adopts the picture record layer that dissolves in fountain solution or printing ink solvent, non-then image region by be contained in printing machine on impression cylinder or blanket cylinder contact and by the machinery removal.But, according to the shortcoming at the image recording method that prints toning system of traditional ultraviolet light or visible light be picture record layer even still unfixing after exposure.Therefore, this system need compare the measuring method of trouble, and promptly plate presoma will be placed under complete darkness or the constant temperature, is installed on the printing machine up to it.
On the other hand, another trend in this field is, the digital image information technology is popularized widely, and wherein picture information is carried out electronic processing, storage and output by computing machine.And various new visual output system of this digital technology that can keep is used in practice.Under such environment, a large amount of notices concentrates on computing machine one forme technology, by the high directed radiation line such as laser beam, uses digital image information, rather than uses the offset printing film, just can directly be made a plate by exposure scanning plate presoma.The plate presoma product that is fit to this technology has been a very important techniques problem.
Therefore, simplify the plate-making operation and maybe needn't handle the needs that promptly use forme, become more important, require environmental protection and suitable digitizing all important than common with dried.
Be easy to therein adopt in the method for platemaking of scan exposure in conjunction with digital technology, promising especially method is to utilize the method for platemaking of a kind of image recording element with high output solid state laser device, as semicondcutor laser unit or YAG laser aid, because the recent price of this class device is lower.In traditional method for platemaking, the photosensitive printing plate presoma is carried out the image exposure with lower medium illumination, promptly generate image thereby photochemical reaction takes place on the surface of plate presoma.The result is exactly, thereby the mode recording picture of image variation with physical property takes place on the plate presoma surface.On the other hand, in the method with the high-energy-density exposure, for example expose with a high output laser aid, direct set exposure is carried out with a large amount of luminous energy in the zone that is exposed, and just can convert the energy efficient of exposure to heat energy.This heat energy has caused that various heat energy change, and such as the variation of chemical change, phase change, form and structure etc., and these variations are used to recording picture.In other words, picture information is imported with luminous energy, laser beam for example, and should be recorded by the reaction that heat energy causes by image.Usually, this register system of high-energy-density exposure of utilizing is meant the hot type record, and becomes heat energy to be meant the photo-thermal conversion transform light energy.
Method for platemaking with the hot type recording element has great advantage, be exactly the hot type photosensitive material be photostable basically under common illuminance, and photographic fixing is not always carried out picture record by high exposure illumination.In other words, being used to when the hot type photosensitive material under the situation of recording picture, is safe under the room light before exposure, and in addition, they always do not require visual photographic fixing yet after exposure.Therefore, if with this class picture record layer, this picture record layer can be made into dissolving or undissolved by the hot type exposure, if and printing the image that toning system is applicable to removal exposure picture record layer in the plate-making step, after exposure picture record layer is by indoor light exposure a little while, there is the image technology system of recording picture not to be subjected to the influence of development (removing non-image region) operation just to become possibility so.
Like this, utilize the hot type record to be applicable to that with regard to making that design is a kind of lithographic plate presoma on the seal toning system becomes possibility.
Need a kind of method of in the substrate of hot type record, making lithographic printing-plate, here this method there is a kind of scheme, on at the bottom of the hydrophilic group, provide hydrophobic picture record layer exactly, this picture record layer is suitable for the hot type exposure, to change its dissolubility or diffusivity, and if desired, non-image region can be removed by wet mode of developing.
As the example that is fit to a kind of lithographic plate presoma of the above-mentioned method of mentioning, the plate presoma of hot type record is disclosed among the Jap.P. JP-B-46-27919 (term used herein " JP-B " means " the disclosed Japanese patent application in examination back " here), each plate presoma has the recording layer on hydrophilic support, this recording layer can improve dissolubility by heat energy, or the alleged positive job record layer in hydrophilic support, the recording layer that special composition is more especially arranged, its composition has carbohydrate or melamine-formaldehyde resin.
But disclosed every kind of recording layer does not all have enough thermo-responsive photosensitiveness, and therefore this light sensitivity is inadequate to the hot type scan exposure.In addition, it is that resolving power is very little between its water wettability and the hydrophobicity that an actual problem is arranged, and perhaps before and after exposure, changes in solubility is very little.If this resolving power is very weak, being used in the seal toning system, to make forme just very difficult basically.
In addition, disclose this class lithographic plate presoma among the patent No. WO98/40212, it has a hydrophilic layer, and this layer is included in the suprabasil transition metal oxide colloid that scribbles ink-receiver layer, described ink-receiver layer comprises the photo-thermal conversion agent, and this plate presoma can not need develop and makes a plate.Wherein, contain the hydrophilic layer of transition metal oxide colloid, can remove to peel off (ablation) by the heat of emitting at the photo-thermal conversion agent of exposure area.Though the photo-thermal conversion agent is present in the side of substrate,, be again that substrate is advanced in emission from the heat of absorbing light conversion, thereby it just can not be used to contain the peeling off of hydrophilic layer of colloid effectively.Therefore, this plate presoma has the low shortcoming of light sensitivity.In addition, Jap.P. JP-A-55-105560 (term " JP-A " here means and do not examine disclosed Japanese patent application) and WO94/18005 patent all disclose the lithographic plate presoma that hydrophilic layer is arranged, and this hydrophilic layer is to peel off to be similar to the above-mentioned mode that scribbles the lipophilicity photothermal transformation layer in substrate.Because above-mentioned same, these presomas also are that light sensitivity is low.
In order to improve the low shortcoming of thermal sensitive lithographic printing front body light sensitivity of aforesaid heat-peelable, disclose a kind of lithographic plate presoma in WO99/19143 and WO99/19144 patent, this lithographic plate presoma contains the thermal cross over agent in the hydrophilic colloid layer as the upper strata.These plate presomas have improved light sensitivity really, but be added to the film quality that photo-thermal conversion agent in the hydrophilic layer has reduced hydrophilic layer, cause printing capability to descend, perhaps, in some cases, damage the character of hydrophilic layer and can draw a new problem, in printing process, can catch the stain of printing ink exactly at non-image region.
In addition, when another problem of peeling off of the temperature-sensitive presoma of the lithographic printing-plate that these are commonly used is that the scum silica frost of peeling off spreads, can cause the dirty of laser explosure device and optical system, therefore reduce the ability of image dissection, and more very be the outside that scum silica frost can be diffused into device.
Described in the European patent EP 0816070 and peeled off control.According to this patent; the thermal photography element has and comprises hydrophilic polymer water-soluble or the hydroexpansivity protective seam; this protective seam is on the imaging layer on the hydrophilic support; also comprise hydrophobic thermoplastic polymer particles; and photo-thermal conversion agent; under certain condition, they can be diffused in the hydrophile adhesive mass.And the protective seam that provides on imaging layer control is peeled off.But, above this image recording method of being adopted in the described patent, comprising can be by the hydrophobic thermoplastic polymer particle of thermosol, this heat is emitted by laser radiation, laser radiation is to imaging layer insoluble in water; And the zone do not shone of laser, dissolve by developing and remove by water or aqueous solution, thereby leave irradiation area as image region.Wherein, produce in a parallel manner by the polymer beads of thermosol at irradiation area and to peel off for the second time, again dirty image region, thus cause printing quality destroyed.At this situation, protective layer used in this peeling off of control.On the contrary, this method of peeling off comprises by peeling off removes the laser radiation zone, and the result is that the scum silica frost of generation is inevitable in stripping means.Therefore, as a kind of scum silica frost diffusion (scum-scatter) control survey, on exposure device, install and peel off dross trap and used very extensively.But, both having made drip catcher had been installed, scum silica frost pollutes and is difficult to avoid fully.
Utilize the advantage of the digital information system of hot type picture record be need not the situation of any film under, can directly make from the prefabricated original copy of taking a picture (camera-ready copy), thereby this plate-making can be used on the machine effectively, and development operation also can be omitted, but also has shortcoming above-mentioned.
Summary of the invention
Therefore, an object of the present invention is to solve the problem that exists in the hot type method for platemaking of traditional employing laser radiation recording picture.More specifically be, an object of the present invention is to provide a kind of thermal sensitive lithographic printing front body, it has short-term scan exposure adaptability, can directly install on the printing machine and need not be through developing and printing operation, and can guarantee printing life-span that lithographic printing-plate is high and lithographic printing-plate is not had scum silica frost (that is, not having dirty point).
Another object of the present invention provides a kind of thermal sensitive lithographic printing front body, the peeling off of heat-sensitive layer when it can guarantee to control laser beam lithography (diffusion (scatter)), thus reduce exposure device and comprise the pollution of the optical system of light source.
Of the present invention also have another purpose to provide a kind of thermal sensitive lithographic printing front body, it can be guaranteed to utilize and peels off as imaging means, and do not destroy the character of forme, these character comprise the reduction light sensitivity, and when laser beam lithography, can control the diffusion that heat-sensitive layer is peeled off scum silica frost, thereby the pollution of guaranteeing exposure device and optical system reduces.
Concentrate the conclusion of research above-mentioned purpose to be as us, have been found that the formation of the water-soluble external coating on hydrophilic layer, can be when peeling off, the diffusion of control hydrophilic layer, and can not influence light sensitivity, printing capability, printing adaptability on the contrary and print development adaptability.In addition, find, when the water-soluble external coating that contains the photo-thermal conversion agent during, can not reduce printing capability and printing adaptability and keep ISO, and can control peel off (diffusion) of hydrophilic layer as the top layer of hydrophilic layer.Based on these discoveries, can realize the present invention.
More specifically, following is embodiment of the present invention:
1. a thermal sensitive lithographic printing front body is included in a suprabasil hydrophilic layer that has printing ink acceptance surface or scribble ink-receiver layer; Described plate presoma also has a water-soluble external coating on hydrophilic layer, and described hydrophilic layer is three-dimensional cross-linked hydrophilic layer, and its heating region is to be easy to remove by fountain solution or printing ink in printing operation.
2. according to the thermal sensitive lithographic printing front body of embodiment 1, wherein, described external coating comprises a photo-thermal conversion agent.
3. according to the thermal sensitive lithographic printing front body of embodiment 1 or 2, wherein, one deck hydrophilic layer and ink-receiver layer comprise a photo-thermal conversion agent at least.
4. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, described crosslinked hydrophilic layer comprises at least a oxide of beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and the colloid of hydroxide compound of being selected from.
5. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, described crosslinked hydrophilic layer comprises and at least aly is selected from the oxide of beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and the colloid of hydroxide compound, and hydrophilic resin.
6. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, described crosslinked hydrophilic layer comprises the colloid of at least a oxide that is selected from beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and hydroxide compound and is used for the crosslinking chemical of this colloid.
7. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, described crosslinked hydrophilic layer comprises at least a oxide of beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and the colloid of hydroxide compound of being selected from, hydrophilic resin and the crosslinking chemical that is used for this colloid.
8. according to the thermal sensitive lithographic printing front body of embodiment 5 or 7, wherein, hydrophilic resin is the macromolecular compound with hydroxyl or carboxyl.
9. according to the thermal sensitive lithographic printing front body of embodiment 5 or 7, wherein, hydrophilic resin is hydroxy alkyl acrylate homopolymer or multipolymer, or hydroxy alkyl methacrylate homopolymer or multipolymer.
10. according to the thermal sensitive lithographic printing front body of embodiment 6 or 7, wherein, crosslinking chemical is tetraalkoxysilane, trialkoxysilyl propyl group-N, N, the initial hydrolysis condensation product of N-trialkyl-ammonium halide or aminopropyl trialkoxy silane.
11. according to the arbitrary thermal sensitive lithographic printing front body of embodiment 4-10, wherein, described colloid is the colloidal sol that contains the hydrolysis condensation product of dialkoxy silicane, trialkoxy silane, tetraalkoxysilane or its potpourri.
12. according to the arbitrary thermal sensitive lithographic printing front body of embodiment 4-10, wherein, this described colloid is the colloidal sol of hydrolysis condensation product that contains the tetrol salt (tetraalkoxide) of aluminium, titanium or zirconium.
13. according to the arbitrary thermal sensitive lithographic printing front body of embodiment 4-10, wherein, colloid is the colloid that contains organic solvent solution.
14. according to the thermal sensitive lithographic printing front body of embodiment 13, wherein, organic solvent is methyl alcohol or ethanol.
15. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, substrate is Polyethylene Terephthalates or polycarbonate film.
16. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, substrate is to scribble the aluminium of the organic polymer resin of accepting printing ink or base steel sheet.
17. according to embodiment 1,2 or 3 thermal sensitive lithographic printing front body, wherein, substrate is aluminium or the base steel sheet with the oleophylic plastic film laminate.
18. according to embodiment 1,2 or 3 thermal sensitive lithographic printing front body, wherein, substrate is to scribble the paper of the organic polymer that printing ink accepts or the paper of oleophylic plastic film laminate.
19. according to embodiment 1,2 or 3 thermal sensitive lithographic printing front body, wherein, described external coating comprises photo-thermal conversion agent and water soluble resin.
20. according to the thermal sensitive lithographic printing front body of embodiment 2, wherein, described photo-thermal conversion agent is the water-soluble dye that absorption is arranged at irradiation area, or the surface is the pigment of water soluble compound covering.
21. according to the thermal sensitive lithographic printing front body of embodiment 20, wherein, described water-soluble dye is to have at least a cyanine dye that is selected from sulfonic group, its alkali metal salt and its amine salt.
22. according to the thermal sensitive lithographic printing front body of embodiment 1,2 or 3, wherein, the thickness of described external coating is 0.05-4.0 μ m.
23. according to embodiment 1,2 or 3 thermal sensitive lithographic printing front body, wherein, the thickness of described crosslinked hydrophilic layer is 0.1-3 μ m.
According to embodiment of the present invention, photo-thermal conversion agent in the external coating is emitted heat under laser beam lithography, the liberated heat three-dimensional cross-linked hydrophilic layer that will be out at present under the coating is converted to a kind of like this state then, promptly because the present state of external coating need not develop and peel off (diffusion), still remove thereafter by the fountain solution or the printing ink of usefulness for very easy quilt.Below present ink-receiver layer, be released (promptly by peeling) through the zone of heat conversion then, thereby form image region.Although the details of this action principle also is not proved, expressed above-mentioned phenomenon with phrase " stripping type is removed or discharged " in the present invention.In fact, peel off (diffusion) of hydrophilic layer is to be controlled by the external coating that shows as than the upper strata, and to be attached to the hydrophilic layer of ink-receiver layer, the imaging ability can reduce when printing.
In the present invention, from the hydrophilic layer that the ink-receiver layer stripping type discharges, when printing, remove by fountain solution or printing ink.Naturally enough, before hydrophilic layer discharged the removal of (promptly by peeling) zone, external coating had just been removed by fountain solution.When removing external coating, the hydrophilic layer that discharges with stripping type also has been removed.When hydrophilic layer is removed, expose at the ink-receiver layer of lower floor, just form image region.Therefore on the other hand, the unexposed zone of plate presoma still keeps its water wettability, still accepts water and repels printing ink.Use this way, the plate presoma of exposure just is contained on the printing machine and develops, and it can carry out printing operation simultaneously.In plate-making, contrast traditional lithographic printing-plate, forme of the present invention requires not carry out the developer wet process.In other words, lithographic printing-plate can be not treated and be made.
Exposing from plate presoma is installed to this section period on the printing machine to forme, and forme is placed on a few hours in the air, and the hand processing that perhaps is stained with printing ink can make oleophilic substance be attached to the forme surface, and these all are frequent the generations.But the present invention has protected hydrophilic layer, and this hydrophilic layer can become non-image region, and therefore this hydrophilic layer scumming can not take place by the adhesive force as the water-soluble external coating opposing oleophilic substance of the superiors is provided when printing.
In addition, the photo-thermal conversion agent that adds external coating to makes the heat that wherein produces directly be transferred in the hydrophilic layer under the external coating, thus the same can the being used effectively when heat energy of being emitted almost is added in the hydrophilic layer with conversion agent.The result is exactly almost the thing that light sensitivity does not take place to reduce in the present invention.Therefore, controlling in the present invention by the diffusion of peeling off the hydrophilic layer that causes just becomes possibility, and light sensitivity is maintained.By control by peeling off the diffusion that causes, laser explosure device and comprise that the optical system of light source just do not pollute, and, install on device that arbitrary to peel off the capture scum device especially just dispensable.
Therefore, need not handle the basic problem that direct seal carving version produces, when this external coating is provided, just solve.
As already mentioned, exposing from plate presoma is installed to this section period on the printing machine to forme, and forme is placed on a few hours in the air, and the hand processing that perhaps is stained with printing ink can make oleophilic substance be attached to the forme surface, and these all are frequent the generations.Measure the pollution that is not subjected to stick oleophilic substance in the legacy system that carries out development treatment for protection, in the last viscose step of processing procedure, the forme surface is coated with a water-soluble substances and protects.On the other hand, the forme of not handling never adopts the sort of pollution control survey device; The result is that hydrophilic surface layer has directly been polluted, and scumming appears in trend.But, become the hydrophilic layer of non-image region according to the present invention, can be used as the water-soluble external coating protection of the superiors, in case be subjected to sticking of lipophilicity substance, therefore just the scumming phenomenon can not take place when printing.
Use this way, need not handle other basic problem that direct seal carving version produces, when this external coating is provided, also solved.
Method for making of the present invention is described in detail as follows:
Water-soluble coating among the present invention, it includes a kind of resin that is selected from water-soluble organic or inorganic macromolecular compound, can be removed at an easy rate in printing.Employed here water-soluble organic or inorganic resin (macromolecular compound), it is the resin that when coating and drying, can become film, for example, these resins comprise, polyvinyl acetate (PVA) (percent hydrolysis is at least 65%), polyacrylic acid and its alkaline metal or amine salt, acrylic copolymer and its alkaline metal or amine salt, polymethylacrylic acid and its alkaline metal or amine salt, polymethyl acid copolymer and its alkaline metal or amine salt, polyacrylamide and polyacrylamide copolymer.Poly-hydroxyethyl acrylate, polyvinyl pyrrolidone and polyvinyl pyrrolidone multipolymer, poly-(vinyl methylether), tygon methyl-copolymer-maleic anhydride, poly-(2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid) and its alkaline metal or amine salt, poly--2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid multipolymer and its alkaline metal or amine salt, Arabic gum, cellulose derivative (as carboxymethyl cellulose, carboxyethyl cellulose and methylcellulose) and modifier, white dextrin (whitedextrin), amylopectin and zymolytic etherificate dextrin.These resins use with its two or more potpourris according to required purpose.
In addition, in the present invention, this photo-thermal conversion agent can be contained in the water-soluble external coating, simultaneously, also can be included in hydrophilic layer and/or the ink-receiver layer.
In other words, the photo-thermal conversion agent can be comprised in hydrophilic layer and/or the ink-receiver layer, simultaneously, also can be included in the water-soluble external coating.
Employed photo-thermal conversion agent can be the material that some can absorb the light of 700nm or bigger wavelength among the present invention, therefore available various pigment and dyestuff.The example that can be used for the pigment of top conversion agent comprises commercially available pigment, and these pigment are described in Color index (C.I.) handbookIn: published that Nippon GanryoGijutu Kyokai edits in 1977 " Saishin Ganryo Binran " (meaning is " a up-to-date pigment handbook "), published by CMC Shuppan in 1986 " Saishin Ganryo Ohyo Gijutu " (meaning is that " up-to-date pigment should Use technology ")And published by CMC Shuppan in 1984 " Insatu Ink Gijutu " (meaning is " a seal The brush ink technology ")
Type about pigment, mineral black, brown pigment, red, purple dye, blue pigment, green pigment, fluorescent pigment, metallic powdery pigment and keyed jointing polymeric dye are particularly comprised following available pigment: insoluble azo colour by example, azo lake pigment, condense AZO pigments, the chelating AZO pigments, phthalocyanine color, anthraquinone pigment, north and perynone pigment, thioindigo color, quinacridone pigment, dioxazines pigment, isoindolinone pigment, quinophthalone pigment, the dyeing mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment and carbon black.
These pigment can not need surface treatment just to use, and perhaps use after surface treatment.The example of surface treatment method comprises: the method for coating hydrophilic or oleophilic resin on the surface of pigment, the method of on the surface of pigment, sticking a surfactant, a bonding reactive material on the surface of pigment (as, silica sol, aluminium colloidal sol, alkane silicone couplet, epoxy compound, polyisocyanate compounds) method.These surface treatment methods are published at MyukiShobo " Kinzoku Sekken no Seishitu to Ohyo " (meaning be " character of metallic soap and Use "), published by CMC Shuppan in 1984 " Insatu Ink Giiutu " (meaning is " an off-set oil The China ink technology ")And published by CMC Shuppan in 1986 " Saishin Ganryo Ohyo Gijutu " (meaning is " a up-to-date pigment applications technology ")In description is arranged.In these pigment, preferably can absorb infrared ray or near infrared pigment, particularly also have infrared ray or the near infrared irradiation capability that adapts to the laser aid emission because comprise their plate presoma.
Because pigment absorbs infrared ray or near infrared ray, it is exactly favourable adopting the carbon black of carbon black, the carbon black that is coated with hydrophilic resin and silica sol modification.In these pigment, process hydrophilic resin or silica sol surface-treated carbon black are just especially suitable, and be compatible or dispersed preferably because it has with water soluble resin, and hydrophilic nmature is not had retroaction.
For the grain size of pigment, need it in the scope of 0.01-1 μ m, preferably in the scope of 0.01-0.5 μ m.When the dispersed color particle, can adopt tradition to be used for the dispersion technology of ink product or product of toner.Here the decollator example of Shi Yonging has ultrasound wave fan diffuser, sand mill, masher, pearl mill, super comminutor, bowl mill, impeller, decollator, KD mill, colloid mill, Dynatron, three rod-type roll mills and pressure kneader.It was published by CMC Shuppan in 1986 " Saishin Ganryo Ohyo Gijutu " (meaning is " a up-to-date pigment applications technology ")The middle detailed description in detail.
On the other hand, for dyestuff, known dyestuff in commercially available dyestuff and the document (as, published the Senryo Binran (meaning is " a dyestuff handbook ") that Yuki Gousei Kagaku Kyokai edits in 1970) all available.These examples comprise: azo dyes, metal cooperate azo dyes, pyrazolone azo dyes, anthraquinone dye, phthalocyanine dye, carbonium dyestuff, quinoneimine dye, methine dyes and cyanine dye.In these dyestuffs, especially preferably can absorb infrared ray or near infrared dyestuff, this is to have infrared ray or the near infrared irradiation capability that adapts to the laser aid emission because comprise their plate presoma.
More specifically, be used for absorption infrared ray of the present invention or near infrared dyestuff and comprise, cyanine dye is as open in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829 and JP-A-60-78787; Methine dyes, open in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595; Naphthoquinone dyestuff, open in JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940 and JP-A-60-63744; The squarylium dyestuff is as open in JP-A-58-112792; Be disclosed in the BrP 434,875 cyanine dye and at United States Patent (USP) 4,756, disclosed dyestuff in 993, it is with following formula (I) and (II) expression:
Figure C0013701900131
R wherein 1, R 2, R 3, R 4, R 5And R 6Be respectively to replace or unsubstituted alkyl; Z 1And Z 2Be respectively that atom is substituted or unsubstituted benzene or naphthalene nucleus (being phenyl or naphthyl) fully; L replaces or unsubstituted methine, substituting group on each methine can be the alkyl that contains no more than 8 carbon atoms, halogen atom or amino, or the substituting group on two different methines can replace or unsubstituted cyclohexene or cyclopentene ring in conjunction with forming, wherein the replacement on the ring or can be alkyl or the halogen atom that contains no more than 6 carbon atoms; X is an anionic group; N is 1 or 2; And in addition, at least a R1, R2, R3, R4, R5, R6, Z1 and Z2 have the substituting group that contains acid moieties or its alkaline metal or amine salt.
R wherein 11Be to replace or unsubstituted alkyl, replace or unsubstituted aryl, or replacement or unsubstituted heterocyclic group; R 12And R 15Be respectively the hydrogen atom or the group that can be replaced by hydrogen atom; R 13And R 14Be respectively hydrogen atom, halogen atom replaces or unsubstituted alkoxy, or replacement or unsubstituted alkyl, but gets rid of R 13=R 14The situation of=H; R 16And R 17Be respectively to replace or unsubstituted alkyl, replace or unsubstituted aryl acyl group or sulfonyl, perhaps R 16And R 17Mutually combine and be formed into nonmetal 5-or 6-unit ring.
In addition, at United States Patent (USP) 5,156, disclosed near-infrared absorbing emulsion also is favourable in 938.In addition, at United States Patent (USP) 3,881, the alkyl benzo (sulfo-) of disclosed replacement in 924-pyrans father-in-law salt, disclosed three first thiapyran father-in-law salt in Jap.P. JP-A-57-142645 (United States Patent (USP) 4,327,169), at Jap.P. JP-A-58-181051, JP-A-58-220143, JP-A-5941363, JP-A-59-84248, JP-A-59-84249, disclosed pyrans father-in-law compound among JP-A-59-14603 and the JP-A-59-146061, disclosed cyanine dye in JP-A-59-216146 is in U.S. Pat 4,283, disclosed five first sulfo-pyrans father-in-law salt in 475, disclosed pyrans father-in-law compound and Epolight III-178 among Jap.P. JP-B-5-13154 and the JP-B-5-19702, Epolight III-130 and Epolight III-125 (trade name, the product of Epolin company limited) product is particularly advantageous.
In these dyestuffs, the water-soluble cyanine dye of preferred following formula (I).
The example of this class cyanine dye is described below:
Figure C0013701900151
Figure C0013701900171
These dyestuffs and pigment are the 1-70 weight % introducings with the total solid that is used to form the overcoating combinations thing, preferred 2-50 weight %, and under the situation of dyestuff, more preferably 2-50 weight %, preferred especially 2-30 weight %, and under the situation of pigment, preferred especially 2-50 weight %.When the dyestuff that adds or the ratio of pigment are lower than above-mentioned scope, light sensitivity will step-down; And when being higher than above-mentioned scope, this layer will be inhomogeneous, and the durability of this layer also reduces.
When coating Aquo-composition formation external coating, major part can be added in the Aquo-composition to guarantee the homogeneity of coating for the surfactant of non-ionic surfactant.The example that is applicable to the non-ionic surfactant of this purpose comprises: sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, glyceryl monostearate, the inferior ethene nonyl phenylate of polyoxy and polyoxyethylene lauryl ether.
The ratio that is fit to that non-ionic surfactant accounts for the total solid of external coating is 0.05-5 weight %, preferred 1-3 weight %.
The suitable depth that is used for external coating of the present invention is 0.05 μ m-4.0 μ m, preferred 0.1 μ m-1.0 μ m.When external coating is too thick, remove it by printing operation and will spend the long time, and a large amount of eluted water soluble resin has influenced the quality of fountain solution and caused that printing bothers, and goes out band and does not have printing ink at image-text area such as cylinder.On the other hand, when external coating is too thin, film quality is reduced.
Hydrophilic layer of the present invention with three-dimensional crosslinking structure is the layer that is insoluble to fountain solution, and this fountain solution is used to adopt the lithographic plate of water and/or printing ink to handle, and this just requires this hydrophilic layer to comprise colloid as described below.Particularly, this colloid comprises the composition of the sol/gel body converting system of the oxide of beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony or transition metal or oxyhydroxide.In some cases, colloid can be the colloid that comprises the complex of two or more above-mentioned above-mentioned chemical elements.In colloid, the atom of this above-mentioned class chemical element forms reticulate texture by oxygen atom, and they also have the not hydroxyl and the alkoxy of bonding simultaneously.In the step of hydrolytic condensation, have a large amount of active alkoxy and hydroxyls in the colloid, and in course of reaction, the size of colloidal solid has increased in the early stage, and the inertia that becomes.The diameter of colloidal solid is 2nm-500nm normally.Under the situation of silicon dioxide, the spherical colloidal particle diameter that uses among the present invention is 5nm-100nm.In addition, have the colloidal solid of 100nm * 10nm shape size,, also can effectively use in the present invention as in the aluminium glue body.
In addition, have the colloidal solid of pearl necklace shape, its length is 50nm-400nm, and is that the spheric grain of 10nm-50nm is made by diameter, all can use in the present invention.
The above-mentioned colloid of mentioning can use separately, also can mix use with hydrophilic resin.In order to improve cross-linking reaction, can in colloid, add crosslinking chemical.
In normal circumstances, comprise stabilizing agent in the colloid.As stabilizing agent, the compound that has anionic group can be joined in the positively charged colloid, the compound that will have cation group simultaneously joins in the electronegative colloid.For example, the stabilizing agent that joins in the electronegative colloidal silica is an aminated compounds, and those stabilizing agents that are added in the positively charged aluminium glue body are strong acid, example hydrochloric acid and acetic acid.These colloids of great majority can at room temperature form transparent membrane in the time of on being coated onto substrate.But, can not only rely on the evaporation of colloid solvent to realize the complete gel of colloid.The colloid coating is heated to the temperature that can remove destabilizing agent then, thereby forms closely crosslinked three-dimensional structure, thereby and forms the hydrophilic layer that the present invention suits.
Another kind of feasible way is, can be directly from raw material (as, two, three and/or tetraalkoxysilane) generate suitable collosol state by hydrolysis-condensation reaction, and needn't be with above-mentioned stabilizing agent.And the colloidal sol of Sheng Chenging can itself form be coated onto in the substrate like this, and is dry then and finish reaction.In this case, can under with the lower temperature of the situation of stabilizing agent, obtain three-dimensional crosslinking structure.
In addition, also be applicable to the present invention by the suitable hydrolysis condensation product colloid that it is stable of diffusion in organic solvent.From this class colloid,, just can form three-dimensional cross-linked film only by evaporating solvent.And can just can at room temperature realize drying, solvent such as methyl alcohol, ethanol, propyl alcohol, butanols, glycol monoethyl ether, ethylene glycol monoethyl ether or MEK by selecting lower boiling solvent.Particularly, the colloid in methyl alcohol or alcohol solvent is easy to solidify at low temperatures, and this is useful in the present invention.
With the hydrophilic resin that above-mentioned colloid uses, preferably have the resin of hydrophilic radical, preferably as: the hydrophilic radical of hydroxyl, carboxyl, hydroxyethyl, hydroxyphenyl, amino, amino-ethyl, aminopropyl and ethyloic.
The example of this class hydrophilic resin comprises: Arabic gum, casein, gelatin, starch derivative, carboxymethyl cellulose and sodium salt thereof, acetyl cellulose, mosanom, vinyl acetate-maleic acid, styrene-maleic acid copolymer, polyacrylic acid and salt thereof, polymethylacrylic acid and salt thereof, methacrylic acid hydroxyethyl ester homopolymer and multipolymer, hydroxyethyl acrylate homopolymer and multipolymer, hydroxypropyl methacrylate homopolymer and multipolymer, acrylic acid hydroxypropyl ester homopolymer and multipolymer, hydroxyethyl methacrylate butyl ester homopolymer and multipolymer, hydroxybutyl acrylate homopolymer and multipolymer, polyglycol, the hydroxyl acrylic polymers, polyvinyl alcohol (PVA) and degree of hydrolysis are at least 60 weight %, the hydrolysed polyvinyl acetate of preferred at least 80 weight %, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, methacrylamide homopolymer and multipolymer, methacrylamide hopolymer and multipolymer, and N hydroxymethyl acrylamide homopolymer and multipolymer.
In these hydrophilic resins, hydroxyl but water-insoluble polymer, as, special preferable methyl hydroxyethyl acrylate homopolymer and multipolymer, and hydroxyethyl acrylate multipolymer.
Be used in combination above-mentioned hydrophilic resin and colloid, the suitable ratio of water-soluble hydrophilic resin is 40 weight % or lower of hydrophilic layer total solid, and wherein the suitable ratio of water-insoluble hydrophilic resin is 20 weight % or lower of hydrophilic layer total solid.
These hydrophilic resins can itself form use, but are the purpose of the ability of impressing that increases institute's formation forme, and can use the crosslinking chemical of non-colloid for hydrophilic resin.The example of the crosslinking chemical of hydrophilic resin comprises: formaldehyde, glyoxal, the initial hydrolysis condensed products of polyisocyanate and four oxyalkylsiloxane and dimethylolurea and hexamethylolmelamine.
Except the colloid and above-mentioned hydrophilic resin of above-mentioned oxide or oxyhydroxide, promote the crosslinked crosslinking chemical of colloid can join in the hydrophilic layer of the present invention.The suitable example of this crosslinking chemical comprises tetraalkoxysilane, trialkoxysilyl propyl group-N, N, the initial hydrolysis condensation product of N-trialkyl ammonium halide and aminopropyl trialkoxy silane.This crosslinking chemical suitable ratio in the total solid of hydrophilic layer is 5 weight % or lower.
For hydrophilic layer of the present invention, the water wettability photo-thermal conversion agent that joins in the above-mentioned external coating also can add to increase thermal sensitivity.Special photo-thermal conversion agent of wishing is water-soluble infrared absorbing dye, particularly above-mentioned formula (I) cyanine dye representative and that contain sulfonic group or sulfonic alkaline metal or amine salt.The pigment that adds as the photo-thermal conversion agent or the suitable ratio of dyestuff are the 1-70 weight % for the total solid in the hydrophilic layer, preferred 2-50 weight %, and under the situation of dyestuff, more preferably 2-50 weight %, preferred especially 2-30 weight %, and under the situation of pigment, preferred especially 2-50 weight %.In the present invention, when the photo-thermal conversion agent joins in the external coating, if necessary, this photo-thermal conversion agent can join in the hydrophilic layer, and the amount of photo-thermal conversion agent is comparable usually little.When addition was lower than aforementioned range, photonasty reduced, and when it was higher than aforementioned range, the hydrophilic nmature of hydrophilic layer was destroyed, and had reduced its homogeneity and permanance.
The suitable thickness that is used for the coating of the three-dimensional cross-linked hydrophilic layer of the present invention is 0.1 μ m-3 μ m, preferred 0.5 μ m-2 μ m.When this coating is too thin, the permanance variation of hydrophilic layer, and the forme that obtains has the relatively poor ability of impressing.On the other hand, when coating is too thick, need lot of energy with from as discharging hydrophilic layer with stripping type the ink-receiver layer of lower level.In other words, when laser is used to expose, need long making the image time, thereby reduced the throughput rate in the plate-making.When making image, when thickness is about 0.5 μ m, need 300-400mJ/cm with the semiconductor laser of the common type that is purchased 2Energy, when thickness is about 1.5 μ m, need 400-500mJ/cm 2Energy.
Substrate with printing ink acceptance surface or coating ink-receiver layer of the present invention can be used as the stable one-tenth sheet material of two dimension.The suitable example of this material comprises paper, with the oleophylic plastics (as tygon, polypropylene, polystyrene) paper of lamination, metal substrate is (as aluminium, zinc, copper, nickel or stainless substrate), the above-mentioned metal substrate of the organic polymer resin of printing ink is accepted in coating, plastic foil is (as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate, cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, the film of polycarbonate or Pioloform, polyvinyl acetal), the above-mentioned plastic foil of organic polymer resin of printing ink is accepted in coating, with and on the above-mentioned metal of accepting printing ink be paper lamination or vapor deposition or plastic foil.
In these materials, the aluminium or the stainless steel substrate of the organic polymer resin of printing ink accepted in the substrate of preferably using as polyethylene terephthalate film, polycarbonate membrane, coating, and with the aluminium or the stainless steel substrate of lipophilicity plastic foil lamination.
Be applicable to that aluminium substrate of the present invention is pure aluminium substrate or the aluminium alloy substrate that contains the external metal of trace, the macromolecular compound of printing ink or the plastic foil that lamination is accepted printing ink are accepted in coating in its surface.The example of the external metal that contains in aluminium alloy is exemplified as silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium.The content of these external metals in alloy is 10 weight % or lower.But, can utilize the suitable hitherto known and widely used aluminium substrate that is selected from the present invention.
When adopting aluminium substrate to be used for substrate of the present invention, need carry out graining (graining) at substrate surface and handle.When the aluminium substrate coating contained the ink-receiver layer of organic high polymer, graining is handled can guarantee easily that substrate surface is bonded to ink-receiver layer.Before roughening is handled by graining in the aluminium substrate surface, carry out ungrease treatment to remove the oil of rolling from substrate surface with surfactant, organic solvent or aqueous alkali.
The graining on aluminium substrate surface can carry out with several different methods, as mechanical graining method, with the method for electrochemical dissolution graining substrate surface and with the method for chemical devices selective dissolution substrate surface.For mechanical graining method, can adopt known method, as ball-milling method, brushing method, abrasive blasting method and polishing method.For chemical graining method, it is favourable adopting in the JP-A-54-31187 disclosed method, and wherein aluminium substrate is immersed in the saturated aqueous solution of mineral acid aluminium salt.For galvanochemistry graining method, the graining method of the electrolytic solution of the acid that contains example hydrochloric acid or nitric acid being used AC or DC is beneficial to employing.In addition, can utilize disclosed electrolysis graining method with acid mixture at JP-A-54-63902.
Wish to carry out the graining processing of above-cited arbitrary method so that the center line average surface roughness (Ra) on aluminium substrate surface is 0.3-1.0 μ m.
The aluminium substrate of graining carries out the alkaline etching processing with containing as the aqueous solution of potassium hydroxide or NaOH, carries out neutralisation treatment (if necessary) again, carries out anodized (if desired) then, to increase corrosion stability.
For the anodized of aluminium substrate, can use the multiple electrolytic solution that can form porous oxide film.Usually, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid and two or more potpourris thereof can be used as electrolytic solution.Suitable concentration of electrolyte is selected according to the type of used electrolytic solution.
The condition of anodized changes according to used electrolytic solution, so they can not be summarized.But according to anodised general standard, suitable concentration of electrolyte is 1-80 weight %, and the temperature of electrolyte solution is 5-70 ℃, and current density is 5-60 ampere/dm 2, voltage is 1-100V, and electrolysis time is 10 seconds-5 minutes.
The appropriate amount of the oxide covering that forms is 1.0-5.0g/m 2, preferred especially 1.5-4.0g/m 2
The thickness that is used for substrate of the present invention is 0.05-0.6mm, preferred 0.1mm-0.4mm, preferred especially 0.15mm-0.3mm.
Organic polymer as the coating of the ink-receiver layer on the substrate surface of the present invention also can form oil-wet film for polymer soluble in solvent.In addition, this polymkeric substance is preferably insoluble in solvent, and described solvent is used to form the coating composition as the hydrophilic layer on upper strata.But, in some cases, can in the used solvent in coating upper strata, the polymkeric substance of swelling be favourable, because they have excellent cohesive to the upper strata.Adopt at another kind under the situation of soluble organic polymer in the used solvent in coating upper strata, wish that this polymer layer solidifies by for example adding crosslinking chemical in advance.
The example of useful organic polymer comprises polyester, polyurethane, polyureas, polyimide, polysiloxane, polycarbonate, phenoxy resin, epoxy resin, phenolics, alkyl phenolic resin, polyvinyl acetate (PVA), acryl resin and acrylic copolymer, tygon phenol, tygon-halogenated phenols, methacrylic resin and methacrylic acid copolymer, acrylamide copolymer, methacrylamide copolymer, polyvinyl formal, polyamide, polyvinyl butyral, polystyrene, cellulose ester resin, Polyvinylchloride and poly-inclined to one side vinylidene chloride.In these polymkeric substance, the resin that contains hydroxyl, carboxyl, sulfonamido or trialkoxysilyl on its side chain is more preferred than other, this is because they all have high cohesive to substrate with as the hydrophilic layer on upper strata, and in some cases, they are easy to solidify by crosslinking chemical.In addition, acrylonitrile copolymer, polyurethane and the multipolymer that contains sulfonamido or hydroxyl on its side chain are beneficial to use, and it can pass through the diazo colours photocuring.
Except above-mentioned polymkeric substance, the resin of novolac resin by the polycondensation reaction between formaldehyde and phenolic compound preparation and cresol resin and the polycondensation reaction preparation by acetone and above-mentioned phenolic compound also is useful, described phenolic compound such as phenol, cresols (metacresol, paracresol or metacresol/paracresol potpourri), phenol/cresols potpourri (phenol/metacresol, phenol/paracresol or phenol/metacresol/paracresol potpourri), phenol-modified dimethylbenzene, tertiary butyl phenol, octyl phenol, resorcinol, 1,2,3-trihydroxy phenol, catechol, chlorophenol (m-Chlorophenol or parachlorphenol), bromine phenol (m-bromophenol or to bromine phenol), salicylic acid and phloroglucin.
As the example of other proper polymer compound, can exemplify that to contain derived from some structural unit and molecular weight that is selected from the monomer of following family (1)-(12) be 1 * 10 4-2.0 * 10 5Multipolymer:
(1) contains aromatic hydroxy acrylamide, Methacrylamide, acrylate and methacrylate, and hydroxy styrenes, as N-(4-hydroxy phenyl) acrylamide, N-(4-hydroxy phenyl)-Methacrylamide, neighbour, between and para hydroxybenzene ethene, neighbour, between and p-hydroxybenzene acrylate and neighbour, with the p-hydroxybenzene methacrylate;
(2) contain the acrylate and the methyl acrylic ester of aliphatic hydroxide radical, as acrylic acid 2-hydroxyethyl ester and methacrylic acid 2-hydroxyethyl ester;
(3) esters of acrylic acid that does not replace or replace is as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, cyclohexyl acrylate, 2-ethyl hexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid 2-chloroethene ester, acrylic acid 4-hydroxyl butyl ester, glycidyl acrylate and N-dimethyl amino ethyl acrylate;
(4) methyl acrylic ester that does not replace or replace is as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, hexyl methacrylate, cyclohexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-chloroethene ester, methacrylic acid 4-hydroxyl butyl ester, glycidyl methacrylate and N-dimethyl amino ethyl methacrylate;
(5) acrylic amide and methacryl amine are as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, the N-methylol methacrylamide, the N-ethyl acrylamide, N-ethyl-methyl acrylamide, N-hexyl acrylamide, N-hexyl methyl acrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methyl acrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl Methacrylamide, N phenyl acrylamide, N-phenyl methyl acrylamide, N-benzyl acrylamide, N-benzyl Methacrylamide, N-nitrobenzophenone acrylamide, N-nitrobenzophenone Methacrylamide, N-ethyl-N phenyl acrylamide and N-ethyl-N-phenyl methyl acrylamide;
(6) ethene ethers is as ethyl vinyl ether, 2-chloroethyl. vinyl ether, hydroxyethyl. and vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ether and Vinyl phenyl ether;
(7) vinyl ester, as vinyl acetic acid esters, vinyl chloride for acetate, vinyl butyrate and vinyl benzoic acid ester;
(8) phenylethylene is as styrene, methyl styrene and 1-chloro-4-methyl-benzene;
(9) vinyl ketones is as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone and phenyl vinyl ketone;
(10) olefines is as ethene, propylene, isobutylene, butadiene and isoprene;
(11) N-vinyl pyrrolidone, N-vinylcarbazole, 4-vinylpridine, vinyl cyanide and methacrylonitrile; And
(12) acrylic amide; as N-(adjacent amino-sulfonyl phenyl) acrylamide; N-(an amino-sulfonyl phenyl) acrylamide; N-(to the amino-sulfonyl phenyl) acrylamide; N-[1-(3-amino-sulfonyl) naphthyl] acrylamide and N-(2-amino-sulfonyl ethyl) acrylamide; the methacryl amine; N-(adjacent amino-sulfonyl phenyl) Methacrylamide; as N-(an amino-sulfonyl phenyl) Methacrylamide; N-(to the amino-sulfonyl phenyl) Methacrylamide; N-[1-(3-amino-sulfonyl) naphthyl] Methacrylamide and N-(2-amino-sulfonyl ethyl) Methacrylamide; undersaturated sulfonamide acrylate; as adjacent amino-sulfonyl phenyl acrylate; between the amino-sulfonyl phenyl acrylate; to amino-sulfonyl phenyl acrylate and 1-(3-amino-sulfonyl phenyl napthyl) acrylate; and undersaturated sulfonamide methacrylate, as adjacent amino-sulfonyl phenyl methyl acrylate; between amino-sulfonyl phenyl methyl acrylate; to amino-sulfonyl phenyl methyl acrylate and 1-(3-amino-sulfonyl phenyl napthyl) methacrylate.
Above-mentioned organic polymer is dissolved in the suitable solvent, be coated in the substrate dry then, thereby an ink-receiver layer is provided in substrate.Wherein, organic polymer although it can be dissolved in separately in the solvent, produces agent, inorganic or organic fine grained, coating surface modifier or plastifier and uses with crosslinking chemical, bonding agent, color usually.Also can add the photo-thermal conversion agent in the ink-receiver layer increasing photonasty, and add the back that is used to expose and form the system (thermally color-producing or color-extinquishins system) that being heated of printing output image produces the color agent or cover color.
The example that is used for the crosslinking chemical of organic polymer comprises diazo resin, aromatics triazo-compound, epoxy resin, isocyanate compound, block isocyanate compound, four alkoxyl silicones, the initial hydrolysis condensation product of aldehyde compound and methylol compound.
For the bonding agent that is suitable in ink-receiver layer, diazo resin is favourable, because it all has excellent cohesive to substrate and ink-receiver layer.In addition, silane coupling agent, isocyanate compound and titanium type colour coupler also are useful.
Produce agent for color, can use common dyestuff and pigment.Particularly, the example of suitable dyestuff comprises Rhodamine 6G chloride, Rhodamine B chloride, crystal violet, peacock green oxalate, oxazines-4-perchlorate, quinizarin, 2-(Alpha-Naphthyl)-5-phenyl-oxazines and coumarin-4; And the example of suitable pigment comprises triphenhlmethane dye, diphenylmethane dye, oxazine dye, not the ton dyestuff, the imino group naphthoquinone dyestuff, azomethine dyes and anthraquinone dye, it is by Oil Yellow #101, Oil Yellow #103, the molten powder #312 of oil, solvent green BG, solvent blue BOS, solvent blue #603, nigrosine BY, nigrosine BS, nigrosine T-505 (above-mentioned all substances are Orient Kagaku Kogyo K.K product), the pure gorgeous indigo plant of alkalescence, crystal violet (CI42555), methyl violet (CI42535), ethyl violet, methylene blue (CI52015), patent ethereal blue (Sumitomo MikuniKagaku K.K. preparation), gorgeous indigo plant, methyl green, erythricine B, basic fuchsin, m-cresol purple, alkaline bright yellow O, 4-is to diethylamino phenylimino naphthoquinones and cyano group-to diethylamino phenyl-monoacetylaniline.In addition, it is favourable also can using at JP-A-62-293247 and the disclosed dyestuff of JP-A-9-179290.
When the material of above-mentioned generation color was added in the ink-receiver layer, its ratio that accounts for the total solid component in receiving layer was generally the about 10 weight % of about 0.02-, the about 5 weight % of preferably about 0.1-.
In addition, can use known fluorine-containing surfactant and silicone surfactant as coating surface modifier.More specifically, the surfactant that contains perfluoroalkyl or dimethyl siloxane is useful, because they can align the condition of coating surface.
Useful in the present invention inorganic or organic fine powder comprises that particle diameter is cataloid and the colloidal aluminum of 10nm-100nm, and this overall diameter is greater than nonactive particle such as silica dioxide granule, the silica dioxide granule with hydrophobic surface, alumina particles, titanium dioxide granule, other heavy metal particles, clay and the mica of colloid.These inorganic or organic fine powders join ink-receiver layer can increase cohesive as the three-dimensional cross-linked hydrophilic layer on upper strata, thereby has increased the ability of impressing of the forme that obtains.The proper ratio of these fine powders in ink-receiver layer is 80 weight % or littler of total solid component, preferred 40 weight % or littler.
Ink-receiver layer of the present invention also can contain the flexible plastifier that is useful on the generation coated film, if desired.The example that is applicable to the plastifier of this purpose comprises polyglycol, tributyl citrate, diethyl phthalate, dibatyl phithalate, phthalic acid dihexyl, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, oleic acid tetrahydrofuran ester and acrylic or methacrylic acid oligomer or polymkeric substance.
In order to differentiate image and the non-image region after the exposure, it is favourable adding the system that produces color or cover color in ink-receiver layer of the present invention.Example as this system, can exemplify and be used in combination thermal acid generator such as diazo-compounds or diphenyl iodnium, and leuco dye (as colourless peacock green, leuco crystal violet or colourless crystallization violet lactone), and be used in combination thermal acid generator and pH color change dyestuff (as ethyl violet or the pure gorgeous blue BOH of alkalescence).In addition, be used in combination acid developing dye and acid adhesive, disclosed as EP897134, also be effective.In this case, bonding by adding thermal destruction producing the lactone body in the dyestuff of form assembling, thereby from coloured change to colourless.
The generation color that is added is 10 weight % or lower of total solid component in the receiving layer with the proper ratio of covering colour system, preferred 5 weight % or lower.
In order to increase thermal sensitivity, ink-receiver layer of the present invention also can contain the photo-thermal conversion agent.The photo-thermal conversion agent that is applicable to this situation is oleophylic dyestuff and pigment, although they can be infrared absorbing dye and above-mentioned pigment.Wherein preferred especially carbon ink and those lipophilicity cyanine dyes that are selected from formula (I) representative.The example of this lipophilicity cyanine dye is as described below:
The proper ratio of the photo-thermal conversion agent that is added (being dyestuff or pigment) is the 1-70 weight % of total solid component in the ink-receiver layer, preferred 2-50 weight %, under the situation of dyestuff, more preferably 2-50 weight %, preferred especially 2-30 weight %, and under the situation of pigment, preferred especially 2-50 weight %.
When the ratio of dyestuff that is added or pigment is higher than the aforementioned upper limit, the then homogeneity of this layer and permanance variation, and be lower than down in limited time when ratio, reduced light sensitivity.
Be applicable to that the example by being coated with the solvent that forms ink-receiver layer of the present invention comprises that alcohols is (as methyl alcohol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycol monoethyl ether, propylene glycol monomethyl ether and ethylene glycol monoethyl ether), ethers is (as tetrahydrofuran, glycol dimethyl ether, Propylene Glycol Dimethyl Ether and tetrahydrofuran), ketone is (as acetone, MEK and diacetone), ester class (as methyl acetate and glycol monomethyl methyl monoacetate), amide-type is (as formamide, the N-NMF, pyrrolidone and N-Methyl pyrrolidone), gamma-butyrolacton, methyl lactate and ethyl lactate.These solvents can use separately or use with its two or more potpourris.In the coating solution of preparation ink-receiver layer, the concentration that is adjusted in the solvent total component (total solids content that comprises adjuvant) to 1-50 weight % be suitable.The coating that forms ink-receiver layer can not only be carried out with above-mentioned organic solvent, and also available aqueous emulsions is carried out.When the latter, the emulsion concentration range is that 5-50 weight % is suitable.
Ink-receiver layer of the present invention is generally at least 0.1 μ m in coating and dried thickness, although its not restriction especially.Under the situation that ink-receiver layer is provided on the metal substrate, the thickness of suitable layer is at least 0.5 μ m, because this layer is also as heat insulator.When ink-receiver layer was too thin, wherein the thermal diffusion of Chan Shenging was to metal substrate; Therefore, reduced light sensitivity.Under the situation of hydrophilic metal substrate, need wearing quality for ink-receiver layer, and the ability that therefore this layer does not have safety to impress when it is too thin.On the other hand, adopting under the situation of plastic foil as substrate, it only needs the bonding coat of ink-receiver layer as the upper strata, so this layer have thickness thinner when adopting metal substrate, and concrete thickness is at least 0.05 μ m.
Adopt the method for platemaking of above-mentioned thermal sensitive lithographic printing front body as follows then.
Lithographic plate presoma directly is carried out to the thermal photography of image by for example thermal head, or carry out the exposure of photo-thermal conversion hysteria, as in the 700-1200nm infrared-ray of solid state laser, semiconductor laser, high illumination flashlamp such as xenon discharge tube or infrared lamp emission, exposing.
Under exposure status, Free Region exposure or scanning method are made image.The regional exposure method is a kind ofly to shine plate presoma with infrared ray or high illumination flashlamp such as xenon discharge tube, produces the method for heat by the photo-thermal conversion.When the regional exposure light source that adopts such as infrared lamp, suitable exposure, although it changes with exposure intensity, before the image of printing was adjusted, according to regional exposure intensity, this exposed usually at 0.1-10J/cm 2In the scope, preferred 0.1-1J/cm 2When using transparent substrates, exposing operation also can be undertaken by the rear side of substrate from substrate.Wish to select this exposure intensity to make that previous exposure intensity is the 0.01-1 millisecond by the time shutter, preferred 0.01-0.1 millisecond reaches.When irradiation time was long, needing increased exposure intensity, had competitive relation because heat energy produces the rate of diffusion of the heat energy of speed and generation.
In scan exposure, can use the light source of the laser beam that can produce rich infrared (infrared-rich), and make image by laser beam flying plate presoma with the picture information adjustment.The example that is applicable to laser beam sources wherein comprises semicondcutor laser unit, He-Ne laser aid, He-Cd laser aid and YAG laser aid.The suitable laser of scan exposure is output as 0.1-300W.But when exposing with impulse laser unit, the highest 1000W at least that is output as, the device of preferred 2000W is effective.Under these laser scanning situations, according to the regional exposure intensity before the adjustment of printed image information, suitable exposure is 0.1-10J/cm 2, 0.3-1J/cm preferably 2
Behind the image exposure, plate presoma of the present invention can be contained on the printing machine, and need not to carry out any other processing.Carry out printing operation with printing ink and water, remove external coating by fountain solution, and simultaneously, the exposure area of also having removed hydrophilic layer.Therefore, by removing hydrophilic layer, obtain exposing the zone, ink-receiver layer is accepted printing ink exposing the zone, makes it and can print.
Now, the present invention sets forth in more detail by the following example.But, the invention is not restricted to these embodiment.
Embodiment
Example I-1
(preparation aluminium substrate)
Contain the nylon (6 of the rolled sheet (rolled sheet) of the thick JISA1050 aluminum of the 0.24mm of 99.5 weight % aluminium, 0.01 weight % copper, 0.03 weight % titanium, 0.3 weight % iron and 0.1 weight % silicon with rotation, 10-nylon) aqueous suspension of brush and 20 weight %400 order purmice stone (by Kyoritsu Yogyo preparation) carries out surperficial graining processing, and water thoroughly washs then.This substrate is 5g/m by being immersed in etching in the 15 weight % sodium hydroxide solutions (containing 4.5 weight % aluminium) until the aluminium amount of dissolving 2, wash with circulating water then.Etched like this substrate neutralizes with 1 weight % nitric acid, and the electric current at anode is 160 coulombs/dm then 2Condition under, by using 10.5V anode voltage and 9.3V cathode voltage (current ratio r=0.90 thereon, the square wave of AC wave shape voltage disclosed current waveform in JP-B-58-5796) carries out the coarse processing of electrolytic surface in 0.7 weight % aqueous solution of nitric acid (containing 0.5 weight % aluminium).After washing with water, aluminium substrate by at 35 ℃, floods etching in the 10 weight % sodium hydrate aqueous solutions again, is 1g/m until the aluminium amount of dissolving 2, and then washing.In addition, by being immersed in decontamination (desmut) in the 30% weight percent sulfuric acid aqueous solution that is heated to 50 ℃, wash with water then.
In addition, the aluminium substrate of handling like this is at 35 ℃ 20 weight % aqueous sulfuric acids (aluminium content: carry out anodised perforated membrane shaping processing with the DC electric current 0.8 weight %) in.More specifically, be 13A/dm in current density 2Under carry out electrolysis, and the control electrolysis time is to form 2.7g/m 2Anode oxide film.
The substrate of Chu Liing washes with water like this, is immersed in the sodium silicate aqueous solution of the 0.2 weight % that is heated to 70 ℃ 30 seconds, washes with water and dry.
The aluminium substrate that obtains like this is 0.30 with the reflection density that Macbeth reflection-densitometer RD920 measures, and the center line average surface roughness is 0.58 μ m.
(the synthetic organic polymer that is used for ink-receiver layer)
Be equipped with in the three-necked bottle of stirrer, condenser and tap funnel at 200ml; put into 4.61g (0.0192mole) N-(to the amino-sulfonyl phenyl) Methacrylamide, 2.94g (0.0258mole) Jia Jibingxisuanyizhi, 0.80g (0.015mole) vinyl cyanide and 20gN; the N-dimethyl acetamide; stir, be heated to 65 ℃ by hot bath simultaneously.In this potpourri, add 0.15g polymerization initiator V-65 (trade name, Wako PureChemical Industries, Ltd. product), and in temperature remains on 65 ℃ nitrogen stream, stirred 2 hours.In the reaction mixture that obtains; dripped 4.61g N-(to the amino-sulfonyl phenyl)-Methacrylamide, 2.94g Jia Jibingxisuanyizhi, 0.80g vinyl cyanide, N again through 2 hours by separating funnel; the potpourri of N-dimethyl acetamide and 0.15gV-65 (Wako Pure Chemical Industries, the polymerization initiator of Ltd. preparation).After dripping, potpourri stirred 2 hours at 65 ℃ again.After reaction is finished, add 40g methyl alcohol, cooling is also under agitation poured in 2 premium on currency.After stirring 30 minutes again, the filtering reaction mixture, drying obtains the 15g white solid.Determine to have obtained N-(to the amino-sulfonyl phenyl) methacrylamide copolymer that weight-average molecular weight is 53,000 (are standard with styrene) by gel permeation chromatography.
(preparation printing ink is accepted substrate)
3g aforementioned N-(to the amino-sulfonyl phenyl) methacrylamide copolymer in batches is dissolved in the mixed solvent of being made up of 9.5g gamma-butyrolacton, 3g methyl lactate, 22.5g MEK and 22g propylene glycol monomethyl ether, and passes through rod-type spreader (bar coater) with 24ml/m 2Coating weight be coated on the aforementioned aluminium substrate.Then, at 1 minute dry coating of 100 ℃ of heating.Thereby, prepared that to have dried overlay capacity be about 1g/m 2The aluminium substrate of ink-receiver layer.
(preparation of thermal sensitive lithographic printing front body)
10% ethylene glycol monomethyl ether solution homopolymer (weight-average molecular weight: 250 of 1g methacrylic acid 2-hydroxyethyl ester, 000), the 3g methyl alcohol silicon dioxide (colloid that in methyl alcohol, contains 30 weight %10-20nm silica dioxide granules, by Nissan Chemicals Industries, Ltd. prepare) and the 16g methanol mixture, with 24ml/m 2Coating weight be coated in the suprabasil aforementioned ink-receiver layer, then 100 ℃ of dryings 1 minute.Thereby forming dried overlay capacity on ink-receiver layer is about 1g/m 2Three-dimensional cross-linked hydrophilic layer.
On this hydrophilic layer, (weight-average molecular weight: the aqueous solution that solution 25,000), the water-soluble cyanine dye of 0.2g (1-31) (it is formerly set forth) and 0.025g polyoxyethylene nonylplenyl ether are formed is with 12ml/m by the 20g5% acrylate homopolymer 2Coating weight coating, 100 ℃ of dryings 2 minutes, therefore forming dried overlay capacity on hydrophilic layer was about 0.6g/m then 2External coating.Thereby prepared thermal sensitive lithographic printing front body.
(preparation lithographic printing-plate)
Aforementioned lithographic plate presoma is installed on the 40W Trend Setter (the forme erector (plate setter) of the semiconductor laser of 40W emission 830nm light is housed) of Canadian CREO Corp. preparation, and uses 300mJ/cm on it 2Laser energy.Therefore, be contained in the Harris printing machine, and carry out printing operation as the etchant of the fountain solution except that printing ink with the isopropanol water solution that contains 10 volume % with the plate presoma of laser radiation.Can obtain 10,000 high-quality printed matters of no scum silica frost with this forme.
Example I-2
Same way as by example I-1 prepares thermal sensitive lithographic printing front body, except 3g methyl alcohol silicon dioxide 4.5g20 weight %ZrO 2.SiO 2, the colloid methanol solution of Glassca401 (trade name, Nichiban Kenkyusho product) replaces.Under the identical condition of example I-1, this plate presoma that exposes is contained in the Harris printing machine, carries out printing operation then.Can obtain 10,000 high-quality printed matters of no scum silica frost.
Example I-3
Same way as by example I-1 prepares thermal sensitive lithographic printing front body, and except the consumption of methyl alcohol silicon dioxide changes to 4.5g by 3g, the consumption of the ethylene glycol monomethyl ether solution of 10% methacrylic acid 2-hydroxyethyl ester homopolymer changes to 1.5g by 1g.The dried overlay capacity of the crosslinked hydrophilic layer of Zhi Bei plate presoma is about 1.5g/m like this 2This plate presoma is installed on the 40W Trend Setter (the forme erector of the semiconductor laser of 40W emission 830nm light is housed) of Canadian CREO Corp. preparation, and uses 450mJ/cm on it 2Laser energy.Therefore, be contained in the Harris printing machine, and carry out printing operation as the etchant of the fountain solution except that printing ink with the isopropanol water solution that contains 10 volume % with the plate presoma of laser emission.Can obtain 25,000 high-quality printed matters of no scum silica frost.
Example I-4
Same way as by example I-1 prepares thermal sensitive lithographic printing front body, (weight-average molecular weight: ethylene glycol monomethyl ether solution 200,000) replaces by the multipolymer of 1g10% methacrylic acid 2-hydroxyethyl ester/methyl methacrylate (70/30 weight %) except the ethylene glycol monomethyl ether solution of 1g10% methacrylic acid 2-hydroxyethyl ester homopolymer.Under the identical condition of example I-1, this presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.Can obtain 15,000 high-quality printed matters of no scum silica frost.
Example I-5
Same way as by example I-1 prepares thermal sensitive lithographic printing front body, (weight-average molecular weight: ethylene glycol monomethyl ether solution 300,000) replaces by the multipolymer of 2g10% methacrylic acid 2-hydroxyethyl ester/acrylic acid (90/10 weight %) except the ethylene glycol monomethyl ether solution of 1g10% methacrylic acid 2-hydroxyethyl ester homopolymer.Under the identical condition of example I-3, this presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.Can obtain 20,000 high-quality printed matters of no scum silica frost.
Implement I-6～I-10
The printing ink that is similar to example I-1 preparation is accepted substrate, and the following printing ink for preparing is respectively accepted substrate:
Replacement is at the used N-of example I-1 (to the amino-sulfonyl phenyl)-methacrylamide copolymer; in example I-6, adopt phenoxy resin " Phenototo YP-50 " (trade name; Toto KaseiK.K. product); in example I-7, adopt vinyl-formal resin " Denka Formal#200 " (trade name; ElectroChemical Industry Co.; Ltd. product); in example I-8, adopt urethane resin " Estan#5715 " (trade name; Monsanto Corp. product); in example I-9, adopt saturated conjugated polyester resin " KemmitK-1294 " (trade name; Toray Industries Inc. product); and in example I-10, adopt methyl methacrylate/methacryloxypropyl triethoxysilane (60/40 weight %) multipolymer (weight-average molecular weight: 85,000).Various resins are dissolved in the mixed solvent of being made up of 37 weight portion MEKs and 20 weight portion propylene glycol monomethyl ethers with the amount of 3 weight portions, again to wherein adding 0.04 weight portion fluorochemical surfactant " Megafac F-177 " (trade name, Dai-Nippon Ink﹠amp; Chemicals, the Inc product).Zhi Bei various solution are with 24ml/m like this 2Amount, be coated on the rod-type spreader on the aluminium substrate of example I-1 preparation.Then, at 1 minute dry coating of 100 ℃ of heating, be about 1g/m thereby on the aluminium substrate surface, form dried overlay capacity 2Ink-receiver layer.Prepare thermal sensitive lithographic printing front body by example I-1 same way as, except the substrate for preparing is replaced by the aluminium substrate of above-mentioned preparation respectively in example I-1.Under the same terms of example I-1, various plate presomas are exposed, and are installed in the Harris printing machine, carry out printing operation then.The result can obtain 10,000 high-quality printed matters of no scum silica frost.
Example I-11
Same way as by example I-1 prepares thermal sensitive lithographic printing front body, except replace the aluminium substrate of example I-1 preparation with the thick pet film of 0.2mm.Under the identical condition of example I-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.The result can obtain 10,000 high-quality printed matters of no scum silica frost.
Example I-12
Following coating composition is with 24ml/m 2Amount, be coated on the rod-type spreader on the aluminium substrate of example I-1 preparation.Then, 100 ℃ of dryings 1 minute, be about 1g/m thereby form dried overlay capacity 2The aluminium substrate of ink-receiver layer.
The coating composition that is used for ink-receiver layer
N-(4-hydroxyphenyl) Methacrylamide/propylene acyl cyanide/benzyl acrylate/methacrylic acid (26/13/49/12 weight) multipolymer (weight-average molecular weight: 75,000) 3g
The hexafluorophosphoric acid ester condensates 0.3g of 4-diazo diphenyl amino formaldehyde
Leuco crystal violet 0.15g
Methyl alcohol 10g
Glycol monoethyl ether 17g
Then, total substrate surface of formation exposes to produce three-dimensional crosslinking structure therein by 3KW UV lamp.Zhi Bei substrate is used to replace the aluminium substrate of example I-1 coating ink-receiver layer like this.By the same way as of example I-1, except this replacement, the preparation thermal sensitive lithographic printing front body.
Under the identical condition of example I-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.The result can obtain 10,000 high-quality printed matters of no scum silica frost.
Example I-13
In the substrate of the ink-receiver layer that is coated with example I-1, with 24ml/m 2Amount coating coating solution with following component.And be about 1g/m to form dried overlay capacity in 1 minute 100 ℃ of dryings 2Three-dimensional cross-linked hydrophilic layer.In addition, the external coating that this hydrophilic layer coating example I-1 is identical is with the preparation thermal sensitive lithographic printing front body.Under the identical condition of example I-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.The result can obtain 20,000 high-quality printed matters of no scum silica frost.
The coating composition that is used for hydrophilic layer
10% methacrylic acid (2-hydroxyethyl) ester homopolymer (weight-average molecular weight: ethylene glycol monomethyl ether solution 1g 250,000)
Methyl alcohol silicon dioxide (colloid that in methyl alcohol, contains 30 weight %10-20 order silica dioxide granules, by Nissan Chemicals Industries, the Ltd. preparation) 3g
Aminopropyltriethoxywerene werene 0.05g
Methyl alcohol 16g
Example I-14
Same way as by example I-1 prepares thermal sensitive lithographic printing front body, except replace the coating solution that is used for external coating of example I-1 with the coating solution with following composition.Under the identical condition of example I-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.The result obtains 10,000 high-quality printed matters of no scum silica frost.
The coating composition that is used for external coating
5% acrylate homopolymer (weight-average molecular weight: 250,000)
Solution 20g
Water-soluble cyanine dye I-32 (illustrating in this manual) 0.2g
The inferior ethene nonyl of polyoxy phenylate 0.25g
Example I-15
3g N-(to the amino-sulfonyl phenyl) Methacrylamide/methyl methacrylate/vinyl cyanide/methacrylic acid 2-methylol ester (40/10/30/20 weight %) multipolymer is dissolved in the mixed solvent of being made up of 50g glycol monoethyl ether and 47g MEK, and with 20ml/m 2Amount be coated on the used identical aluminium substrate of example I-1, then 100 ℃ of dryings 1 minute.It is about 0.6g/m that thereby preparation has dried overlay capacity 2The aluminium substrate of ink-receiver layer.
Then, by 18g tetraethoxysilane, 32g ethanol, 32g purified water and 0.02g nitric acid are placed in the beaker, and at room temperature stir and prepared sol solution in 1 hour.Sol solution, 4g10% polyvinyl alcohol water solution " PVA 117 " (trade name by 3g above-mentioned preparation in batches, Kuraray Co., Ltd. aqueous solution (the trade name of 8g20% cataloid " SnowtexC " product),, Nissan Chemicals Industries, Ltd. product), the coating solution formed of 8g purified water and the inferior ethene nonyl of 0.04g polyoxy phenylate, with 20ml/m 2Amount, be coated on by the rod-type spreader on the aluminium substrate of above-mentioned coating ink-receiver layer, then 100 ℃ of dryings 5 minutes.Therefore, forming dried overlay capacity is about 2g/m 2Hydrophilic layer.On this hydrophilic layer, adopt the identical coating of example I-14 that provides in the identical mode of example I-14 to prepare the temperature-sensitive presoma of lithographic printing-plate.This plate presoma is installed on the 40W Trend Setter (the forme erector of the semiconductor laser of 40W emission 830nm light is housed) of Canadian CREO Corp. preparation, and uses 600mJ/cm on it 2Laser energy.Bao Guang plate presoma is contained in the Harris printing machine like this, and carries out printing operation.The result obtains 40,000 high-quality printed matters of no scum silica frost.
Example II-1
(preparation aluminium substrate)
Prepare aluminium substrate by example I-1 same way as.
(the synthetic organic polymer that is used for ink-receiver layer)
By the synthetic organic polymer that is used for ink-receiver layer of the same way as of example I-1.
(preparation printing ink is accepted substrate)
Same way as preparation by example I-1 has the aluminium substrate of ink-receiver layer.
(preparation is used for the temperature-sensitive presoma of lithographic printing-plate)
The methacrylic acid 2-hydroxyethyl ester homopolymer (weight-average molecular weight: 250 of 1g10%, 000) ethylene glycol monomethyl ether solution, the 3g methyl alcohol silicon dioxide (colloid that in methyl alcohol, contains 30 weight %10-20nm silica dioxide granules, by Nissan Chemicals Industries, Ltd. preparation), previous 0.08g cyanine dye (I-31) of setting forth and 16g methanol mixture be coated on the ink-receiver layer on the aforementioned substrates, then 100 ℃ of dryings 1 minute.Thereby forming dried overlay capacity on ink-receiver layer is about 1g/m 2Three-dimensional cross-linked hydrophilic layer.
On this hydrophilic layer, (weight-average molecular weight: 25, the 000) aqueous solution formed of the inferior ethene nonyl of solution and 0.025g polyoxy phenylate 100 ℃ of dryings 2 minutes, is about 0.6g/m thereby form dried overlay capacity on hydrophilic layer then by the 20g5% polyacrylic acid in coating 2External coating.So prepare thermal sensitive lithographic printing front body.
(preparation lithographic printing-plate)
Aforementioned lithographic plate presoma is installed on the 40W Trend Setter (the forme erector of the semiconductor laser of 40W emission 830nm light is housed) of Canadian CREO Corp. preparation, and uses 300mJ/cm on it 2Laser energy.After the radiation, observe the forme surface, thereby confirm to use energy area almost not peel off the vestige of diffusion.This postradiation plate presoma is contained in the Harris printing machine, and carries out printing operation with the isopropanol water solution that contains 10 volume % as the etching agent except that printing ink.The result observes and can obtain 10,000 high-quality printed matters of no scum silica frost.
Comparative example II-1
Prepare thermal sensitive lithographic printing front body by the same way as of example II-1 and be used for contrast, except external coating is not provided.Under the same terms of example II-1, this plate presoma laser emission, and be installed on the identical printing machine, carry out printing operation then.After laser emission, confirm to have produced tangible diffusion owing to peel off hydrophilic layer in radiation areas by observing the forme surface.Although obtained 10,000 printed matters by printing operation, this printed matter has the fingerprint stain, supposes that it is when in printing machine forme being installed, to produce when contacting with the finger that stains printing ink.
Example II-2
Prepare the temperature-sensitive presoma of lithographic printing-plate by the same procedure of example II-1, except 3g methyl alcohol silicon dioxide with 4.5g20 weight %ZrO 2.SiO 2, the colloid methanol solution of Glassca401 (trade name, Nichiban Kenkyusho product) replaces.Under the condition identical with example II-1, this plate presoma exposes.After the exposure, observe the forme surface and confirm using energy area almost not peel off the vestige of diffusion.Bao Guang plate presoma is contained in the Harris printing machine then, carries out printing operation under the identical condition of example II-1.The result can obtain 10,000 high-quality printed matters of no scum silica frost.
Example II-3
The temperature-sensitive presoma for preparing lithographic printing-plate by the same way as of example II-1, except the consumption of methyl alcohol silicon dioxide changes to 4.5g by 3g, the consumption of the ethylene glycol monomethyl ether solution of 10% methacrylic acid 2-hydroxyethyl ester homopolymer changes to 1.5g by 1g, is replaced by previously described cyanine dye (I-32) as the cyanine dye (I-31) of photo-thermal conversion agent.The dried overlay capacity of the crosslinked hydrophilic layer of Zhi Bei plate presoma is about 1.5g/m like this 2This plate presoma is installed on the 40W Trend Setter (the forme erector of the semiconductor laser of 40W emission 830nm light is housed) of Canadian CREO Corp. preparation, and uses 450mJ/cm on it 2Laser energy.Observe the forme surface after the radiation and confirm almost not peel off the vestige of diffusion.The plate presoma of radiation is contained in the Harris printing machine, and carries out printing operation with the etchant of the fountain solution of isopropanol water solution conduct except that printing ink that contains 10 volume %.The result can obtain 25,000 high-quality printed matters of no scum silica frost.
Example II-4
The temperature-sensitive presoma for preparing lithographic printing-plate by the same way as of example II-1, (weight-average molecular weight: ethylene glycol monomethyl ether solution 200,000) replaces by the multipolymer of 1g10% methacrylic acid 2-hydroxyethyl ester/methyl methacrylate (70/30 weight %) except the ethylene glycol monomethyl ether solution of 1g10% methacrylic acid 2-hydroxyethyl ester homopolymer.Under the condition identical with example II-1, this plate presoma is exposed.After the exposure, observe the forme surface and confirm almost not peel off the vestige of diffusion.Bao Guang plate presoma is contained in the Harris printing machine then, carries out printing operation then under the condition identical with example II-1.The result can obtain 15,000 high-quality printed matters of no scum silica frost.
Example II-5
The temperature-sensitive presoma for preparing lithographic printing-plate by the same way as of example II-1, (weight-average molecular weight: ethylene glycol monomethyl ether solution 300,000) replaces by the multipolymer of 2g10% methacrylic acid 2-hydroxyethyl ester/acrylic acid (90/10 weight %) except the ethylene glycol monomethyl ether solution of 1g10% methacrylic acid 2-hydroxyethyl ester homopolymer.Under the identical condition of example II-3, this plate presoma is exposed.After the exposure, observe the forme surface and confirm almost not peel off the vestige of diffusion.Bao Guang plate presoma is contained in the Harris printing machine then, and carries out printing operation under the identical condition of example II-3.The result can obtain 20,000 high-quality printed matters of no scum silica frost.
Example II-6～II-10
Same way as by example II-1 provides external coating respectively, except polyacrylic acid in example II-6 is replaced (weight-average molecular weight 15 by sodium polymethacrylate, 000), in example II-7, adopt polyvinyl alcohol (PVA) (saponification degree: 88mole%, the degree of polymerization: 1,000), in example II-8, adopt poly-(2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid) (weight-average molecular weight 15,000), in example II-9, adopt polyacrylamide (weight-average molecular weight 10,000), and in example II-10 5% polyacrylic acid aqueous solution by 4.5% poly-ethanol (saponification degree: 98.8mole%, the degree of polymerization: 500) and the potpourri of 0.5% polyacrylic acid aqueous solution (weight-average molecular weight 25,000) replace.The component of other various thermal sensitive lithographic printing front bodies is identical with example II-1.Under the condition identical with example II-1, various plate presoma laser emissions.After the radiation, observe the forme surface and confirm almost not peel off the vestige of diffusion.The plate presoma of various radiation is contained in the Harris printing machine then, and carries out printing operation under the identical condition of example II-1.The result can obtain 10,000 high-quality printed matters of no scum silica frost.
Example II-11～II-15
The printing ink that is similar to example II-1 preparation is accepted substrate, and the following printing ink for preparing is respectively accepted substrate:
Replacement is at the used N-of example II-1 (to the amino-sulfonyl phenyl)-methacrylamide copolymer; in example II-11, adopt phenoxy resin " Phenototo YP-50 " (trade name; Toto Kasei K.K. product); in example II-12, adopt vinyl-formal resin " Denka Formal#200 " (trade name; Electro Chemical Industry Co.; Ltd. product); in example II-13, adopt urethane resin " Estan#5715 " (trade name; Monsanto Corp. product); in example II-14, adopt saturated conjugated polyester resin " KemmitK-1294 " (trade name; Toray Industries Inc. product); and in example II-15, adopt methyl methacrylate/methacryloxypropyl triethoxysilane (60/40 weight %) multipolymer (weight-average molecular weight: 85,000).Various resins are dissolved in the mixed solvent of being made up of 37 weight portion MEKs and 20 weight portion propylene glycol monomethyl ethers with the amount of 3.0 weight portions, again to wherein adding 0.04 weight portion fluorochemical surfactant Megafac F-177 (trade name, Dai-Nippon Ink ﹠amp; Chemicals, the Inc product).Zhi Bei various solution are with 24ml/m like this 2Amount, be coated on the rod-type spreader on the aluminium substrate of example II-1 preparation.Then, at 1 minute dry coating of 100 ℃ of heating, be about 1g/m thereby on aluminium substrate, form dried overlay capacity 2Ink-receiver layer.Prepare thermal sensitive lithographic printing front body by example II-1 same way as, except the substrate for preparing is replaced by the substrate of above-mentioned preparation respectively in example II-1.Under the same terms of example II-1, various plate presomas are exposed, and are installed in the Harrs printing machine, carry out printing operation then.The result can obtain 10,000 high-quality printed matters of no scum silica frost.In addition, after the radiation, observe the forme surface and confirm almost not peel off the vestige of diffusion.
Example II-16～II-18
Prepare printing ink by the identical mode of example II-1 and accept substrate, except their coating compositions that is used for ink-receiver layer separately are different from example II-1, it has also added the cyanine dye as the photo-thermal conversion agent.
More particularly, the formula of various coating compositions is as follows:
N-(to the amino-sulfonyl phenyl) metering system amide multipolymer 3g
Cyanine dye 0.3g
Gamma-butyrolacton 9.5g
Methyl lactate 3g
MEK 22.5g
Propylene glycol monomethyl ether 22g
For aforementioned cyanine dye, cyanine dye (I-33), (I-34) and (I-37) (its oneself sets forth before) are respectively applied for example II-16, example II-17 and example II-18.
Accept in the substrate at these printing ink, be coated with hydrophilic layer identical and identical external coating with example II-3.Therefore the various plate presomas of preparation expose by the plate setter identical with example II-1, make to use 400mJ/cm therein 2Energy, be contained in then on the Harrs printing machine, carry out printing operation.As a result, observe in each case and can obtain 10,000 high-quality printed matters of no scum silica frost.In addition, after the radiation, the observation on forme surface shows does not almost peel off the vestige of diffusion.
Example II-19
Same way as by example II-1 prepares thermal sensitive lithographic printing front body, except replace the aluminium substrate of example II-1 preparation with the thick pet film of 0.2mm.Under the identical condition of example II-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.As a result, observe and to obtain 10,000 high-quality printed matters of no scum silica frost.In addition, after the radiation, the observation on forme surface shows does not almost peel off the vestige of diffusion.
Example II-20
Following coating composition is with 24ml/m 2Amount, be coated on the rod-type spreader on the aluminium substrate of example II-1 preparation.Then, 100 ℃ of dryings 1 minute, be about 1g/m thereby on the aluminium substrate surface, form dried overlay capacity 2Ink-receiver layer.
The coating composition that is used for ink-receiver layer
N-(4-hydroxy phenyl) Methacrylamide/vinyl cyanide/benzyl acrylate/methacrylic acid (26/13/49/12 weight) multipolymer (weight-average molecular weight: 75,000) 3g
The hexafluorophosphoric acid ester condensates 0.3g of 4-diazo diphenyl amino formaldehyde
Leuco crystal violet 0.15g
Methyl alcohol 10g
Glycol monoethyl ether 17g
Then, whole substrate surfaces of formation expose to produce three-dimensional crosslinking structure therein by 3KW UV lamp.Zhi Bei substrate is used to replace the aluminium substrate of example II-1 coating ink-receiver layer like this.By the same way as of example II-1, except this replacement, the preparation thermal sensitive lithographic printing front body.
Under the condition identical with example II-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.As a result, can obtain 10,000 high-quality printed matters of no scum silica frost.In addition, after the exposure, the observation on forme surface shows does not almost peel off the vestige of diffusion.
Example II-21
On the aluminium substrate of the ink-receiver layer that is coated with example II-1, with 24ml/m 2Amount coating have the coating solution of following composition.100 ℃ of dryings was about 1g/m to form dried overlay capacity in 1 minute 2Three-dimensional cross-linked hydrophilic layer.In addition, the external coating that this hydrophilic layer coating example II-1 is identical is with the preparation thermal sensitive lithographic printing front body.Under the condition identical with example II-1, this plate presoma is exposed, and is installed in the Harris printing machine, carries out printing operation then.As a result, can obtain 20,000 high-quality printed matters of no scum silica frost.In addition, after the exposure, the observation on forme surface shows does not almost peel off the vestige of diffusion.
The coating composition that is used for hydrophilic layer
10% methacrylic acid (2-hydroxyethyl) ester homopolymer (weight-average molecular weight: glycol monomethyl 250,000)
Methyl ether solution 1g
Methyl alcohol silicon dioxide (colloid that in methyl alcohol, contains 30 weight %10-20nm silica dioxide granules, by
Nissan Chemicals Industries, the Ltd. preparation) 3g
Aminopropyltriethoxywerene werene 0.05g
Cyanine dye (I-32) 0.13g
Methyl alcohol 16g
Example II-22
3g N-(to the amino-sulfonyl phenyl) Methacrylamide/methyl methacrylate/vinyl cyanide/methacrylic acid 2-methylol ester (40/10/30/20 weight %) multipolymer is dissolved in the mixed solvent of being made up of 5g glycol monoethyl ether and 47g MEK, and with 20ml/m 2Amount be coated on the used identical aluminium substrate of example II-1, then 100 ℃ of dryings 1 minute.It is about 0.6g/m that thereby preparation has dried overlay capacity 2The aluminium substrate of ink-receiver layer.
Then, 18g tetraethoxysilane, 32g ethanol, 32g purified water and 0.02g nitric acid are placed in the beaker, and at room temperature stir and prepared sol solution in 1 hour.Sol solution, 4g 10% polyvinyl alcohol water solution " PVA117 " (trade name by 3g above-mentioned preparation in batches, Kuraray Co., Ltd. 8g20% cataloid " SnowtexC " (trade name product),, Nissan Chemicals Industries, Ltd. the coating solution that the inferior ethene nonyl of aqueous solution product), 0.10g cyanine beam material (I-31), 8g purified water and 0.04g polyoxy phenylate is formed is with 20ml/m 2Amount be coated on the aluminium substrate of above-mentioned coating ink-receiver layer, then 100 ℃ of dryings 5 minutes.Therefore, forming dried overlay capacity is about 2g/m 2Hydrophilic layer.On this hydrophilic layer, adopt and the same way as of example II-3 temperature-sensitive presoma with the identical production of coatings lithographic printing-plate of example II-3.This plate presoma is installed on the 40W Trend Setter (the forme erector of the semiconductor laser of 40W emission 830nm light is housed) of Canadian CREO Corp. preparation, and uses 600mJ/cm on it 2Laser energy.Bao Guang forme is contained in the Harris printing machine like this, and carries out printing operation.As a result, can obtain 40,000 high-quality printed matters of no scum silica frost.In addition, after the exposure, the observation on forme surface shows does not almost peel off the vestige of diffusion.
The problem of the hot type method for platemaking that utilizes laser explosure commonly used can solve by embodiment of the present invention.Particularly, temperature-sensitive plate presoma of the present invention is applicable to the short-term scan exposure, and can be installed on the printing machine and need not to carry out development treatment, just directly carries out printing operation.Forme by presoma preparation of the present invention has the ability of impressing preferably and the vestige that almost do not develop.
In addition, heat-sensitive layer of the present invention can suppress peel off (scattering) that laser explosure produces, and therefore can effectively avoid the pollution of the exposure device that comprises optical system that diffusate causes.
Describe the present invention in detail by specific embodiment, for those skilled in the art, can carry out multiple variation and not depart from its aim and scope with accommodation.

Claims (23)

1. a thermal sensitive lithographic printing front body is included in a suprabasil hydrophilic layer that has printing ink acceptance surface or scribble ink-receiver layer; Described plate presoma also has a water-soluble external coating on hydrophilic layer, and described hydrophilic layer is three-dimensional cross-linked hydrophilic layer, and the heating region of described hydrophilic layer is easy to remove by fountain solution or printing ink in printing operation.
2. according to the thermal sensitive lithographic printing front body of claim 1, wherein, described external coating comprises a photo-thermal conversion agent.
3. eucalyptus is according to the thermal sensitive lithographic printing front body of claim 1, and wherein, described hydrophilic layer and ink-receiver layer comprise a photo-thermal conversion agent.
4. according to claim 1,2 or 3 thermal sensitive lithographic printing front body, wherein, described crosslinked hydrophilic layer comprises the colloid of the compound of at least a oxide that is selected from beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and oxyhydroxide.
5. according to claim 1,2 or 3 thermal sensitive lithographic printing front body, wherein, described crosslinked hydrophilic layer comprises the colloid of the compound of at least a oxide that is selected from plating, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and oxyhydroxide, and hydrophilic resin.
6. according to claim 1,2 or 3 thermal sensitive lithographic printing front body, wherein, described crosslinked hydrophilic layer comprise at least a oxide that is selected from beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and oxyhydroxide compound colloid and be used for the crosslinking chemical of this colloid.
7. according to claim 1,2 or 3 thermal sensitive lithographic printing front body, wherein, described crosslinked hydrophilic layer comprise at least a oxide that is selected from beryllium, magnesium, aluminium, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metal and oxyhydroxide compound colloid, hydrophilic resin and be used for the crosslinking chemical of this colloid.
8. according to the thermal sensitive lithographic printing front body of claim 5, wherein, hydrophilic resin is the macromolecular compound with hydroxyl or carboxyl.
9. according to the thermal sensitive lithographic printing front body of claim 5, wherein, hydrophilic resin is hydroxy alkyl acrylate homopolymer or multipolymer, or hydroxy alkyl methacrylate homopolymer or multipolymer.
10. according to the thermal sensitive lithographic printing front body of claim 6, wherein, crosslinking chemical is tetraalkoxysilane, trialkoxysilyl propyl group-N, N, the initial hydrolysis condensation product of N-trialkyl ammonium halide or aminopropyl trialkoxy silane.
11. according to the thermal sensitive lithographic printing front body of claim 4, wherein, described colloid is the colloidal sol that contains the hydrolysis condensation product of dialkoxy silicane, trialkoxy silane, tetraalkoxysilane or its potpourri.
12. according to the thermal sensitive lithographic printing front body of claim 4, wherein, this described colloid is the colloidal sol of hydrolysis condensation product that contains the tetrol salt of aluminium, titanium or zirconium.
13. according to the thermal sensitive lithographic printing front body of claim 4, wherein, colloid is the colloid that contains organic solvent solution.
14. according to the thermal sensitive lithographic printing front body of claim 13, wherein, organic solvent is methyl alcohol or ethanol.
15. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, substrate is Polyethylene Terephthalates or polycarbonate film.
16. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, substrate is to scribble the aluminium of the organic polymer resin of accepting printing ink or base steel sheet.
17. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, substrate is aluminium or the base steel sheet with the oleophylic plastic film laminate.
18. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, substrate is to scribble the paper of the organic polymer of printing ink acceptance or the paper of oleophylic plastic film laminate.
19. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, described external coating comprises photo-thermal conversion agent and water soluble resin.
20. according to the thermal sensitive lithographic printing front body of claim 2, wherein, described photo-thermal conversion agent is the water-soluble dye that absorption is arranged at irradiation area, or the surface is the pigment of water soluble compound covering.
21. according to the thermal sensitive lithographic printing front body of claim 20, wherein, described water-soluble dye is to have at least a cyanine dye that is selected from sulfonic group, its alkali metal salt and its amine salt.
22. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, the thickness of described external coating is 0.05-4.0 μ m.
23. according to the arbitrary thermal sensitive lithographic printing front body of claim 1-3, wherein, the thickness of described crosslinked hydrophilic layer is 0.1-3 μ m.
CN 00137019 2000-11-20 2000-11-20 Thermal sensitive lithographic printing front body Expired - Fee Related CN1221863C (en)

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CN103317827A (en) * 2012-03-21 2013-09-25 施乐公司 Dampening fluid deposition by condensation in digital lithographic system

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PL1788435T3 (en) * 2005-11-21 2013-09-30 Agfa Nv Method of making a lithographic printing plate
JP5238292B2 (en) * 2007-03-23 2013-07-17 三菱製紙株式会社 Water-developable photosensitive lithographic printing plate material
CN102821969B (en) * 2010-03-26 2014-12-03 富士胶片株式会社 Master planographic printing plate and manufacturing method therefor
CN103587272B (en) * 2013-11-04 2019-01-18 北京中科纳新印刷技术有限公司 A kind of temperature-sensitive grain-free printing plate and the preparation method and application thereof
CN105313517B (en) * 2014-12-19 2017-08-25 乐凯华光印刷科技有限公司 Sensitive lithographic plate version base
CN106364209B (en) * 2016-11-04 2018-11-09 中国科学院理化技术研究所 Thermosensitive treatment-free lithographic printing plate material containing thermosensitive protective layer and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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