CN102540730B - Positive image ultraviolet-computer-to-plate ((UV-CTP) planographic printing plate - Google Patents
Positive image ultraviolet-computer-to-plate ((UV-CTP) planographic printing plate Download PDFInfo
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Abstract
The invention discloses a positive image UV-CTP planographic printing plate, which comprises a plate supporting body, wherein an alkali soluble resin is coated on the supporting body; a positive image photosensitive layer is coated on the alkali soluble resin layer; and the alkali soluble resin comprises an alkali soluble resin, an additive resin and a dye. The plate has the advantages of high photosensitive speed, high developing tolerance, high resolution, high solvent resistance, high printing resistance and the like. The UV-CTP planographic printing plate has high storage stability and can better adapt to the conventional UV-CTP platemaking.
Description
Technical field
The invention belongs to CTP platemaking technology field, be specifically related to a kind of positive image UV-CTP lithographic plate plate.
Background technology
The CTP(Computer To Plate) technology, because of advantages such as its digitizing, high-effect high-quality and easy, environmental protection, replaces traditional simulation plate-making mode gradually, becomes the approach that printing enterprise realizes technology upgrading.The CTP plate-making mode of main flow is divided into thermosensitive CTP, purple laser c TP and UV-CTP three types at present, and wherein UV-CTP can be used the traditional PS plate to carry out directly plate-making operation because it is known as, and obtains Rapid Popularization in market.
The laser energy of the UV-CTP of the market mainstream lower (100-300mw), adopts the multiple laser device to increase energy more, to guarantee the plate-making energy and to publish efficiency, but the manufacturing cost of platemaking machine significantly increased, and even surpasses 50% of total cost.Nonetheless, the traditional PS plate that meets the UV-CTP ctp request also should have higher film speed 50-80mj/cm
2.
The traditional PS version is generally single layer structure, makes with light breakdown type diazo naphthoquinone compounds as photosensitizer.This type of photosensitizer had not only served as and has seen the light decomposed substance but also serve as resistance solvent (stop or slow down film-forming resin-phenolics and dissolve) in alkaline-based developer in formula.The consumption of photosensitizer is larger, hinder molten effect more abundant, and film speed is slower; The molten effect of phase anti-drag is not obvious, and film speed is faster.The ability that plate opposing developer solution corrodes is called alkali resistance.Generally, the alkali resistance of plate is stronger, and resolution and press resistance rate are higher; And alkali resistance is more weak, resolution and press resistance rate are lower.
Up to now, improve the film speed of traditional PS version, usually realize by the consumption that reduces photosensitizer, but the plate alkali resistance obviously reduces, directly have influence on imaging precision and press resistance rate.Therefore, the light sensitivity of traditional PS version and alkali resistance are to be difficult to unified contradiction.In addition, after the photosensitizer consumption in formula significantly reduces, plate also there will be the phenomenon of film speed decay in depositing process.
Summary of the invention
The object of the invention is to solve the above-mentioned technical matters existed in prior art, a kind of positive image UV-CTP lithographic plate plate is provided.
For achieving the above object, the technical solution used in the present invention is as follows:
Positive image UV-CTP lithographic plate plate of the present invention, comprise the plate support, be coated with the alkali soluble resins layer on support, be coated with the positive-type photosensitive layer on the alkali soluble resins layer, described alkali soluble resins layer contains alkali soluble resins, adds resin and illuminating colour.
Described alkali soluble resins adopts any one or more the combination in the organic high molecular polymer of in buck or water solubility or swellability, weight average molecular weight range is between 1000-1000000, be preferably 2000-200000, the quality percentage composition of alkali soluble resins in the alkali soluble resins layer is 40-90%, is preferably 70-90%.
Described interpolation resin is polyurethane polymer, vinyl addition polymer, esters of acrylic acid addition polymer, acetals polymkeric substance or cellulosic polymer, adding the quality percentage composition of resin in the alkali soluble resins layer is 10-60%, is preferably 10-30%.
Described illuminating colour is one or more in Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet or methylene blue, and the quality percentage composition of illuminating colour in the alkali soluble resins layer is 0.5-5%, is preferably 0. 5-2%.
Described alkali soluble resins layer coating weight is 0.5 ~ 1.5g/m
2, be preferably 0.5 ~ 1.0 g/m
2.
Described photographic layer comprises that film-forming resin, interpolation resin, Photoactive compounds, light produce acid source and illuminating colour.
Described film-forming resin is linear phenolic resin, and weight-average molecular weight is 2000-10000, is preferably 2500-7500, M
w/ M
nfor 1.5-20, be preferably 1.5-10.The quality percentage composition of film-forming resin in photographic layer is 20-80%, is preferably 50-80%.
Described interpolation resin is one or more in polyurethane polymer, vinyl addition polymer, esters of acrylic acid addition polymer, acetals polymkeric substance, cellulosic polymer, adding the quality percentage composition of resin in photographic layer is 2-10%, is preferably 5-10%.
Are (the interpolation resin in photographic layer and the interpolation resin of resin bed had any different? in original copy, like well different.The effect of adding resin is to improve the physical strength of coating and physical property, and photographic layer is identical with the interpolation resin effect in resin bed, and compound is also identical)
Described Photoactive compounds is the diazonium naphthoquinone sulphonate compounds, and its esterification parent is the phenols macromolecular compounds such as low molecule polyhydric phenols or linear phenolic resin, and the weight-average molecular weight of esterification parent is 2000-10000, is preferably 2500-4000; M
w/ M
nfor 1.5-20, be preferably 1.5-10, the hydroxy ester rate is the 10-80% of initial hydroxyl, is preferably 20-50%, the quality percentage composition 10-40% of Photoactive compounds in photographic layer, be preferably 10-20%.
Described light produce acid source near ultraviolet band and ultraviolet region the compound of photolysis reactions can occur smoothly, the spectrum induction range is 350-420nm, light produce acid source in photographic layer the quality percentage composition be the 0.1-5 % by weight, be preferably 0.1-2%.
Described illuminating colour is Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet or methylene blue, and quality percentage the see amount of illuminating colour in the alkali soluble resins layer is 0.5-5%, is preferably 0.5-2%.
Positive image UV-CTP lithographic plate plate of the present invention can be for the UV light source as carbon arc lamp, high-pressure mercury-vapor lamp, xenon lamp, metal halide lamp, fluorescent light, tungsten lamp, Halogen lamp LED, helium cadmium laser, argon laser, FD-YAG laser, He-Ne Lasers, semiconductor laser (350nm-450nm), photographic layer is carried out to image exposure.The best is selected the exposure of UV-CTP platemaking machine.
Of the present invention being described in detail as follows:
(1) alkali soluble resins layer
The alkali soluble resins layer contains alkali soluble resins, adds resin and illuminating colour etc.Alkali soluble resins layer coating weight 0.5 ~ 1.5g/m
2, preferred 0.5 ~ 1.0 g/m
2.
Therefore described alkali soluble resins must be able to be dissolved in alkaline-based developer, uses the organic high molecular polymer of in buck solubility or swellability.Organic high molecular polymer as such comprises:
(1) side chain has carboxylic acid group's addition polymer, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc.,
(2) there is carboxylic acid group's acid cellulose derivant at side chain;
(3) at polymkeric substance with addition cyclic acid anhydride on the addition polymer of hydroxyl etc.;
(4) linear phenolic resin and tygon phenol resin, can prepare by polycondensation reaction by linear phenolic resin, and wherein one of monomer must be aromatic hydrocarbons, such as: phenol, orthoresol, metacresol, paracresol, 2, the 5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, bisphenols, bis-phenol-A, triphenol, face ethyl phenol, an ethyl phenol, to ethyl phenol, propyl phenoxy, normal-butyl phenol, tert-butyl phenol, 1-naphthols, beta naphthal.A minimum aldehyde or ketone.Wherein aldehyde can be formaldehyde, acetaldehyde, valeral, benzaldehyde, furfural.Ketone can be acetone, MEK, methyl n-butyl ketone, trioxymethylene.Weight-average molecular weight is determined by GPC.Be advisable with 1000 to 15000,1500 is best to 10000.Linear phenol-aldehyde resin is by aldehyde and phenol condensation.Metacresol/paracresol in phenol/2,5-diphenol/3,5-diphenol/phloroglucin/blending ratio is 40 to 100/0 to 50/0 to 20/0 to 20/0 to 20/.Or phenol/orthoresol/paracresol/blending ratio is 1 to 100/0 to 70/0 to 60/.The tygon phenol resin can be by one or more hydroxy styrenes polymerization, such as: adjacent this ethene of hydroxyl, a hydroxy styrenes, 4-Vinyl phenol, 2-(o-hydroxy-phenyl) propylene, hydroxy phenyl between 2-() propylene, the 2-(p-hydroxybenzene) propylene.Can be by substituting group on these hydroxy styrenes.Such as chlorine, bromine, the halogen atoms such as iodine and fluorine, or the alkyl of C1-4 so that on corresponding resin with these groups.These PEF phenol resin are by one or more hydroxy styrenes polymerization.On it, substituting group can be arranged, be associated with the C1-4 alkyl on the aromatic ring of PEF phenol better, unsubstituted is better.
(5) side chain has carboxylic acid group's polyvinyl acetaldehyde polymkeric substance;
(6) addition polymer that side chain has a phosphate is as addition polymer of containing the vinyl phosphoric acid unit etc.
Described alkali soluble resins can be above-mentioned high molecular polymer, and weight average molecular weight range is between 1000-1000000, and the optimum weight scope is between 2000-200000, any one or several combinations.The percentage by weight of described alkali soluble resins in the alkali soluble resins layer is 40-90%, and the best is 70-90%.
Described interpolation resin plays the whole alkali solubility of adjustment alkali soluble resins layer and the effect of increase alkali soluble resins layer intensity, can use polyurethane polymer, vinyl addition polymer, esters of acrylic acid addition polymer, acetals polymkeric substance, cellulosic polymer etc.Adding the percentage by weight of resin in the alkali soluble resins layer is 10-60%, and the best is 10-30%.
In the alkali soluble resins layer, illuminating colour can be selected from the dyestuffs such as Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet, methylene blue.Preferred Victoria's ethereal blue, alkaline bright blue, solvent blue.The percentage by weight of illuminating colour in the alkali soluble resins layer is 0.5-5%, and the best is 0.5-2%.
(2) photographic layer
Photographic layer comprises that film-forming resin, interpolation resin, Photoactive compounds (PAC), light produce acid source, illuminating colour etc., and the photographic layer coating weight is 0.5 ~ 1.5g/m
2, be preferably 0.5 ~ 1.0 g/m
2.
(1) film-forming resin
In the present invention, the used film forming resin is linear phenolic resin, wherein comprises phenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol (mole ratio 3:7-7:3)-formaldehyde resin, phenol-tertiary butyl phenol (mole ratio 3:1-1.5:1)-formaldehyde resin, metacresol-paracresol (mole ratio 9:1-5:5)-formaldehyde resin, metacresol-orthoresol-a kind of phenols such as formaldehyde resin, the two kinds of phenols linear phenolic resin that even three kinds of phenols and formaldehyde form by the different proportion polycondensation.Their weight-average molecular weight is generally selected 2000-10000, preferably 2500-7500.M
w/ M
nfor 1.5-20, preferred 1.5-10.When molecular weight is greater than 10000, the linearity of phenolics descends, and the degree of branching increases, thereby the solubleness in alkaline developer descends, and development is met difficulty; Molecular weight is too little, in developing process alkali resistance too a little less than, be easy to produce the photodissociation stripping phenomenon, a little less than the pressrun of plate, also have influence on the resolution of plate and the reductibility of site.It is the 20-80 % by weight that the film-forming resin consumption accounts for the photosensitive composition general assembly (TW), preferably the 50-80 % by weight.
(2) add resin
In the present invention, interpolation resin used is 1,2,3,-thrihydroxy-benzene-condensation of acetone resin, and generally this resin polymerization degree is 20-40, shows the shortcoming poor with alkali resistance that wear no resistance during for film-forming resin.The 1,2,3,-thrihydroxy-benzene that the special selective polymerization degree of the present invention is lower-condensation of acetone resin, as adding resin, has following structure:
N means 2-10, and preferably the natural number of 3-6, make positive PS printing plate light sensitive composition and use the sensitive lithographic plate of said composition to have high light sensitivity and large exposure latitude.It is the 2-10 % by weight that interpolation branch consumption accounts for the photosensitive composition general assembly (TW), preferably the 5-10 % by weight.
(3) Photoactive compounds
Photoactive compounds in tradition positive PS printing plate light sensitive component is the diazonium naphthoquinone sulphonate compounds, and its esterification parent can be low molecule polyhydric phenols, can be also the phenols macromolecular compounds such as linear phenolic resin.In the present invention, Photoactive compounds used adopts linear phenolic resin to import parent as macromolecule, with the diazo naphthoquinone sulfonic acid chloride, as graft, the part of hydroxyl esterification of linear phenolic resin is obtained.Synthetic this family macromolecule Photoactive compounds linear phenolic resin used can be the phenolics that above-mentioned film-forming resin is commonly used, example has phenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol (mole ratio 3:7-7:3)-formaldehyde resin, phenol-tertiary butyl phenol (mole ratio 3:1-1.5:1)-formaldehyde resin, metacresol-paracresol (mole ratio 9:1-5:5)-formaldehyde resin, metacresol-orthoresol-a kind of phenols such as formaldehyde resin, two kinds of phenols linear phenolic resin that even three kinds of phenols and formaldehyde form by the different proportion polycondensation.Their weight-average molecular weight is generally selected 2000-10000, and preferably 2500-7500, most preferably be 2500-4000; M
w/ M
nfor 1.5-20, preferably 1.5-10, most preferably be 2.0-4.0.The hydroxy ester rate can be the 10-80% of initial hydroxyl, preferably 20-50%.Synthesized Photoactive compounds use amount in photosensitive composition is 10-40%, is preferably 10-20%, if consumption is too large, hinders molten ability too strong, the difficulty of developing; If consumption very little, hinders molten scarce capacity, alkali resistance is poor, is easy to produce the photodissociation stripping phenomenon, a little less than the pressrun of plate.
(4) light produces acid source
In the present invention, use up produce acid source near ultraviolet band and ultraviolet region (320-450nm) compound of photolysis reactions can occur smoothly, the optimal spectrum induction range is 350-420nm.Optional representative trichloromethyl compound in triazine class is as 1-phenyl-3, the 5 pairs of trichloromethyl triazines, 1-anisyl-3, the 5 pairs of trichloromethyl triazines, 1-are to methoxy styryl-3,5 pair trichloromethyl triazine, 1-methoxy-naphthyl-3,5 pair trichloromethyl triazine etc.It is the 0.1-5 % by weight that the consumption of light product acid source accounts for the photosensitive composition general assembly (TW), preferably the 0.1-2 % by weight.
(5) illuminating colour
In the present invention, background illuminating colour used can be selected from the dyestuffs such as Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet, methylene blue.Can reduce the plate sensitivity owing to considering to ultraviolet absorption, preferably Victoria's ethereal blue, alkaline bright blue, solvent blue.It is the 0.5-5 % by weight that its consumption accounts for the photosensitive composition general assembly (TW), preferably the 0.5-2 % by weight.
The invention provides the double-deck positive-type UV-CTP of a kind of employing plate, lower floor is the alkali soluble resins layer, and upper strata, for having good alkali resistance diazo naphthoquinone light sensitive layer, has solved the contradiction between diazo naphthoquinone system film speed and alkali resistance preferably.This plate has the advantages such as high film speed, high development latitude, high resolving power, solvent resistance and high press resistance rate, and has good storage stability, thereby more be adapted to current UV-CTP mode, makes a plate.
The present invention is owing to adopting said components, and the double-deck positive-type UV-CTP plate made thus, have the advantages such as high film speed, high development latitude, high resolving power and high press resistance rate, and have good storage stability, and its impact of performance is in Table 1.
Embodiment
Below with regard to the concrete manufacturing process of this kind of photo-polymerization type lithographic printing plate, details are as follows.
One, support
The support used in the utility model can be used the aluminium of dimensionally stable or its alloy alloy of silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel (for example with).Usually can use the known material in the past of putting down in writing in aluminium handbook the 4th edition (1990, light metal association distribution).Aluminium plate can be the aluminium plate that adopts common semi-continuous casting method (DC method) to manufacture, and can be also the aluminium plate that adopts the continuous casting rolling process to manufacture in addition.As the method for continuous casting calendering, can use double roller therapy, tape casting method, piece material casting method etc.In alloy, the content of xenogenesis element is below 10 % by weight.The thickness of aluminium plate preferably is about 0.1mm mono-0.6 mm left and right.In addition, plastic foil or the paper of aluminium, aluminium alloy that also can use lamination or evaporation.
1, the surface treatment of support
When support is aluminium plate, usually according to purpose, various processing are implemented in its surface.As general disposal route, at first by aluminium plate is carried out, degreasing or electrolytic polishing are processed and crude removal is processed, and the aluminium surface is cleaned.Then, implement that the mechanical surface roughening is processed or/and the electrochemical surface roughening is processed, give the aluminium plate surface fine concavo-convex.In addition, sometimes also increasing chemical etching processing and crude removal processes.Then, in order to improve the abrasion performance on aluminium plate surface, implement anodized, then as required hydrophilicity-imparting treatment is implemented to or/and sealing of hole is processed in the aluminium surface.
Between the reason, do not bring next into for the treating fluid that makes previous processed and process throughout, the washing that the liquid removal that is preferably adopted nip rolls to carry out and employing injection etc. are carried out.In addition, the overflow waste liquid of the electrolytic solution used in the electrochemical surface roughening can being processed is as the crude removal treating fluid, but the washing that now can omit after crude removal is processed is processed.
(1) degreasing one electrolytic polishing is processed
The rolling oil that exists on aluminium plate, autoxidation epithelium, dirt etc. are removed, turn to purpose to carry out equably electrochemical rough surface, carry out the electrolytic polishing of aluminium plate and process in acidic aqueous solution, or carry out the chemical etching processing of aluminium plate in acid or aqueous alkali.Process the meltage preferred dissolution 1--30g/m of the aluminium plate produced
2.More preferably dissolve 1.5-20g/m
2.
(2) electrolytic polishing is processed
Can use the known aqueous solution for electrolytic polishing.Preferably take the aqueous solution that sulfuric acid or phosphoric acid is main body, the aqueous solution that the phosphoric acid of particularly preferably take is main body.Can be from phosphoric acid 20-90 % by weight (preferably 40-80 % by weight), liquid temperature 10 1 90 ℃ of (preferably 50 1 80 ℃), current density 1-100A/dm
2(preferred 5-80A/dm
2), select in the electrolysis time scope of 180 seconds.Can in phosphate aqueous solution, add 50 % by weight sulfuric acid, chromic acid, hydrogen peroxide, citric acid, hydrofluorite, phthalic anhydride etc.Electric current can be used direct current, pulse direct current or exchange, but preferably continuous direct current.The device that electrolytic processing apparatus can be used the known electrolytic treatments such as flat type groove, star-like groove to use.Flow velocity is with respect to aluminium plate, can for and stream, adverse current any, the scope of dividing from 0.01--10000cm/, choose.
The distance of aluminium plate and electrode is 0.3--10cm, particularly preferably 0.8-2cm preferably.Can use to method for electrically and adopt the direct to electric mode of conductive rollers, also can use and not adopt the indirect to electric mode (liquid is to electric mode) of conductive rollers.The electrode material used, structure can be used known material, the structure used in electrolytic treatments, the preferred carbon of negative electrode material, the preferred ferrite of anode material, indium oxide or paper tinsel.
(3) chemical etching in acid or aqueous alkali is processed
Carry out the chemical etching processing of aluminium plate and can use these known means in acid or aqueous alkali.Liquid temperature is preferably 25-90 ℃, preferably carries out 1-120 processing in second.The concentration of acidic aqueous solution is 0.5-25 % by weight preferably, and the aluminium more preferably dissolved in acidic aqueous solution is 0.5-5 % by weight.The concentration of aqueous alkali is 5-30 % by weight preferably, and the aluminium more preferably dissolved in aqueous alkali is 30 % by weight.
(4) crude removal is processed
After etch processes, when the aqueous solution of using alkali has been carried out chemical etching, due to the Surface Creation dirt at aluminium, therefore general with phosphoric acid, nitric acid, sulfuric acid, chromic acid or contain these nitration mixture in interior acid of more than two kinds and processed (crude removal processing).The acidic aqueous solution used can dissolve 0-5 % by weight aluminium, implements preferred 1-30 of processing time second from normal temperature to 70 ℃ in liquid temperature.In addition, as this acidic aqueous solution, can use the waste liquid of the electrolytic solution used in electrochemical surface roughening processing etc., must be noted that not make the aluminium plate drying, the one-tenth in crude removal liquid analyzes.After the crude removal processing finishes, in order not bring treating fluid into subsequent processing, the liquid that is preferably adopted nip rolls to carry out is removed and is adopted and sprays the washing of carrying out, but, when next operation is same aqueous solution, also can omit washing.
(5) the mechanical surface roughening is processed
In order to obtain good aluminum support, normally to the surface frosted order of aluminium plate, give fine concavo-convex.In this graining, the mechanical surface roughenings such as general known pelletization, brush granulation, tinsel granulation, sandblast granulation are processed, but as a large amount of and continuous processing, brush granulated processed excellence.Specifically, at the slurries of aluminium plate jet surface silica sand, aluminium hydroxide etc., the nylon brush roll rotation that makes bristle footpath 0.2-0.9mm with 50-500rpm, carry out the processing of mechanical surface roughening.The consumption electric power (removing the essence electric power of the mechanical loss of CD-ROM drive motor) of rotation drive motor of the pressing-in force of brush. preferably 0.2-15kw, more preferably 0.5-10kw.
(6) the electrochemical surface roughening is processed
That uses that the electrochemical surface roughening of direct current processes take the aqueous solution that hydrochloric acid or nitric acid is main body, can use the aqueous solution of using in the electrochemical surface roughening that uses common interchange is processed, can in the hydrochloric acid of 1-100g/L or aqueous solution of nitric acid, add 1g/L and there is the use more than 1 of hydrochloric acid or the nitrate compound of salt acid ion to saturated aluminium nitrate, sodium nitrate, ammonium nitrate etc.In addition, take in the aqueous solution that hydrochloric acid or nitric acid is main body the metal of can dissolved iron, containing in the aluminium alloy such as copper, manganese, titanium, magnesium, silicon dioxide.Preferably use and add aluminum chloride, aluminium nitrate so that aluminium ion reaches the liquid of 3-50g/L in hydrochloric acid or nitric acid 0.5-2 % by weight aqueous solution.Preferably 10 1 60 ℃ of temperature, more preferably 25-50 ℃.Use the treating apparatus used in the electrochemical surface roughening of direct current to make
With the device of known use direct current, use anode and the mutual devices of arranging of negative electrode a pair of or more than two pairs.It is the direct current below 20% that the direct current used in the electrochemical surface roughening is preferably used pulsation rate.Current density is 10-200A/dm preferably
2, electric weight when aluminium plate is anode is 10 1 1000C/dm preferably
2.Anode can from ferrite, indium oxide, paper tinsel, on the valve metals such as titanium, niobium, zirconium choice for use in the known oxygen electrode for generating such as compound or plating paper tinsel.Negative electrode can be from carbon, paper tinsel, titanium, niobium, zirconium, stainless steel, the electrode that uses cathode for fuel cell choice for use.
The electrochemical surface roughening use exchanged is processed take the aqueous solution that hydrochloric acid or nitric acid is main body, can use the aqueous solution of using in the electrochemical surface roughening processing exchanged in common use, can add lg/L in the hydrochloric acid of 1--100g/L or aqueous solution of nitric acid and have nitrate ion to saturated aluminium nitrate, sodium nitrate, ammonium nitrate etc., aluminum chloride, sodium chloride, ammonium chloride etc. have at least 1 use of hydrochloric acid or the nitrate compound of salt acid ion.In addition, take in the aqueous solution that hydrochloric acid or nitric acid is main body the metal of can dissolved iron, containing in the aluminium alloy such as copper, manganese, nickel, titanium, magnesium, silicon dioxide.
Preferably use and add aluminum chloride, aluminium nitrate etc. so that aluminium ion reaches the liquid of 3-50g/L in hydrochloric acid or nitric acid 0.5-2 % by weight aqueous solution.Preferably 10-60 ℃ of temperature, more preferably 20-50 ℃.
The AC power ripple used in the electrochemical surface roughening is used marking wave, square wave, platform shape ripple, triangular wave etc., but preferred square wave or platform shape ripple, particularly preferably platform shape ripple.Electric current is from preferred 1-3msec of the time (TP) at 0 arrival peak.If less than 1msec, easily produce what is called inhomogeneous with the processing of the electric shock ripple of the vertical generation of direct of travel of aluminium plate.If TP is larger than 3msec, take in the electrolytic treatments in the nitric acid liquid of representative such as ammonium ion in the electrolytic solution used in the electrochemical surface roughening, the impact that easily is subject to nature to produce the micro constitutent increased, be difficult for carrying out the generation sand holes of homogeneous.
The duty ratio that platform shape ripple exchanges can be used 1:2-2:1, does not use the indirect in electric mode of conductive rollers in aluminium, preferably duty ratio 1:l.The frequency that platform shape ripple exchanges can be used 0.1--120Hz, preferred 50 1 70Hz on equipment.If lower than 50Hz, the carbon electrode of main pole easily dissolves, if larger than 70Hz, easily is subject to the impact of the inductance composition on electric power loop, the power supply cost up.But, when aluminium alloy that use contains the Cu that is greater than 0.1wt%, the preferably interchange of frequency of utilization 0.1--10Hz.The peak value of the current waveform of current density is 10-200A/dm preferably
2.
The electrolytic tank used in the electrochemical surface roughening can be used the electrolytic tank used in longitudinal type, platypelloid type, the known surface treatment such as star-like, and the electrolytic solution passed through in electrolytic tank can be parallel with advancing of aluminium net, also can drive in the wrong direction with it.
Can connect the AC power more than 1 on electrolytic tank.The anode of interchange additional on the aluminium plate relative with main pole and the current ratio of negative electrode are controlled, prevented impressed current anode preferably being set aspect the carbon dissolution of main pole, made the part shunting of alternating current.By rectifier cell or on-off element, the part shunting that makes current value as with 2 central electrodes outside other groove on DC current on the impressed current anode that arranges, can be controlled the participation cathode reaction current value acted on the aluminium plate relative with main pole and the ratio that participates in the current value of anode reaction.On the aluminium plate relative with main pole, ratio when anode (electric weight during negative electrode/electric weight) that participates in the electric weight of anode reaction and cathode reaction preferably 0.3-0.95.
Take in the aqueous solution that nitric acid or hydrochloric acid is major component, use and exchange or direct current, with 10---1000C/dm
2electric weight this aluminium plate is carried out to the processing of electrochemical surface roughening, in acidic aqueous solution, use the platform shape ripple that electric current is 50---70Hz from 0 time to peaking for 1-3msec and frequency to exchange.
(7) (utilizing a sour alkalies) processed in chemical etching
Take will the mechanical surface roughening process, whole of fine concavo-convex sand holes that the electrochemical surface roughening forms in processing, dirt etc. remove as purpose, carry out the chemical etching processing.Liquid temperature is preferably 25-90 ℃, preferably carries out 1-120 processing in second.The concentration of acidic aqueous solution is 0.5-25 % by weight preferably, and the aluminium more preferably dissolved in acidic aqueous solution is 0.5-5 % by weight.The concentration of aqueous alkali is 5-30 % by weight preferably, and the aluminium more preferably dissolved in aqueous alkali is the 1--30 % by weight.Carry out etch processes so that the meltage of aluminium plate reaches 1g/m in acid or aqueous alkali
2above, 30g/m
2below or the meltage of aluminium reach 0.1g/m
2above, 3g/m
2below.
In addition, when the aqueous solution of use alkali is carried out chemical etching, therefore due to the Surface Creation dirt at aluminium, in this case generally with phosphoric acid, nitric acid, sulfuric acid, chromic acid or contain these nitration mixture in interior acid of more than two kinds and carry out etch processes (required crude removal processing).(identical with above-mentioned crude removal record).
(8) anodized
For water-retaining property, the abrasion performance that improves the aluminium plate surface, implement anodized.The electrolyte used in anodized as aluminium plate, if form the porous oxidation epithelium, can be used any electrolyte.Usually use sulfuric acid, phosphoric acid, oxalic acid, chromic acid or their mixed liquor.These electrolytical concentration suitably determine because of electrolytical kind.Anodised treatment conditions become because of used electrolyte, therefore cannot treat different things as the same, if electrolytical concentration is 1--80wt% usually, liquid temperature is 5-70 ℃, and current density is 1--60A/dm
2, voltage 1--100V, electrolysis time 5 seconds---in the scope of 300 seconds, be suitable.Sulfuric acid process is processed by DC current usually, but also can use interchange.The amount of anodic oxide coating is 0.5-10g/m
2scope be suitable.The concentration of sulfuric acid is used 5-30%.In the temperature range of 20-60 ℃, carry out 5-250 second electrolytic treatments.Preferably in this electrolytic solution, contain aluminium ion.Current density now is 1--50A/dm more preferably
2.In the situation that phosphoric acid method, at the concentration 5-50%, the temperature of 30-60 ℃, 10-300 seconds, 1--15A/dm
2current density under processed.The amount of anodic oxide coating is preferably 1.0g/m
2above, more preferably 2.0-6.0g/m
2scope.
(9) hydrophilicity-imparting treatment
After having implemented anodized, as required hydrophilicity-imparting treatment is implemented in the aluminium surface.In the method, by support impregnation, or carry out electrolytic treatments in sodium silicate aqueous solution.(other processing (washing, sealing of hole))
After reason finishes throughout, in order not bring treating fluid into subsequent processing, adopted nip rolls liquid to remove and adopt and sprayed the washing of carrying out.Preferably after anodized, implementing sealing of hole processes.This sealing of hole is processed by dipping in the hydrothermal solution containing hot water and inorganic salts or organic salt and is adopted water vapour to bathe and carries out.
Two, the formation of alkali soluble resins layer
Be coated with the coating of alkali soluble resins layer and carry out drying on the version base of processing, forming the alkali soluble resins layer.
The alkali soluble resins layer composition dissolves, disperses with the solid component concentration of 2-50 % by weight, is applied on the support aluminum substrate and carries out drying.The alkali soluble resins layer coating weight be coated with on the support aluminum substrate preferred dried weight usually is 0.5-1.0g/m
2.Along with coating weight reduces, film strength reduces; Along with coating weight increases, film strength strengthens.
The alkali soluble resins layer composition is dissolved in organic solvent, for being coated with on the support aluminium plate.As solvent used herein, comprise acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, the glycol monomethyl isopropyl ether, ethylene glycol monomethyl ether acetate, 3 one methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate one 3 one methoxy propyl yl acetates, N, the N dimethyl formamide, dimethyl sulfoxide (DMSO), Y mono-butyrolactone, methyl lactate, ethyl lactate etc.These solvents can be used alone or as a mixture
Apparent in order to improve coating, can add surfactant in the alkali soluble resins layer of positive-working lithographic printing plate of the present invention.
As the coating process of alkali soluble resins layer, can use the method for coating scraper (coating rod), the method for extrusion type coating machine, the method for ball coating machine (slide beald coater) etc., but be not limited to these.
Three, the formation of photographic layer
Be coated with the alkali soluble resins layer the version base on photosensitive coated layer coating and carry out drying, finally form positive-working lithographic printing plate of the present invention.
The photographic layer composition dissolves, disperses with the solid component concentration of 2-50 % by weight, is applied on the version base that is coated with the alkali soluble resins layer and carries out drying.In the common preferred dried weight of photographic layer coating weight, be 0.5-1.0g/m
2.Along with coating weight reduces, for the exposure that obtains image, reduce, but film strength reduces.Along with coating weight increases, with exposure, increase, but film strength strengthens.
The photographic layer composition dissolves in various organic solvents for.As solvent used herein, comprise acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, the glycol monomethyl isopropyl ether, ethylene glycol monomethyl ether acetate, 3 one methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate one 3 one methoxy propyl yl acetates, N, the N dimethyl formamide, dimethyl sulfoxide (DMSO), Y mono-butyrolactone, methyl lactate, ethyl lactate etc.These solvents can be used alone or as a mixture.
Apparent in order to improve coating, can add surfactant in the photographic layer of positive-working lithographic printing plate of the present invention.
As the coating process of photographic layer, can use the method for coating scraper (coating rod), the method for extrusion type coating machine, the method for ball coating machine (slide beald coater) etc., but be not limited to these.
Four, exposure and the processing of developing
Positive-working lithographic printing plate plate of the present invention is with for example carbon arc lamp, high-pressure mercury-vapor lamp, xenon lamp, metal halide lamp, fluorescent light, tungsten lamp, Halogen lamp LED, helium cadmium laser, argon laser, FD-YAG laser, He-Ne Lasers, semiconductor laser (350nm-450nm), carry out image exposure to photographic layer.After adopting these known active ray carrying out image exposure in the past, by development treatment, can on aluminium plate support surface, form image.
After image exposure, by the method for developing the photographic layer of exposed portion and alkali soluble resins layer being removed.In the present invention, the development of the above-mentioned developer solution of employing of positive-working lithographic printing plate adopts usual method, 0-60 ℃, preferably at the temperature of 15-40 ℃ of left and right, for example, the positive-working lithographic printing plate that exposure-processed is crossed impregnated in developer solution, with brush wiping etc., carries out.
Carried out like this positive-working lithographic printing plate of development treatment, water wash water, the leacheate that contains surfactant etc., the lipoprotein liquid of not feeling that contains gum arabic or starch derivative etc. carry out aftertreatment.These processing can be carried out to various being used in combination in the aftertreatment of photosensitive lithographic plate of the present invention.The galley prepared by above-mentioned processing can, by adopting the heat treated such as post-exposure processing, roasting, improve printing resistance.Lithographic plate by this processing preparation is installed on offset press, for the printing of multipage.
Below in conjunction with embodiment, the present invention will be described, but the present invention is not subject to the restriction of these embodiment.
Embodiment 1
(1) making of positive-working lithographic printing plate
The curling volume of the aluminium for web-like (curling shape) of the aluminium plate of thick 0.30mm (support) is fixed on the machine of sending.At 10% NaOH for surface treatment, will send the aluminium plate that machine sends continuously from this flood for 60 seconds under 70 ℃, after carrying out etching, after being washed with flowing water, use 20%HN0
3neutralize washing, washing.Use sinusoidal wave alternately waveform electric current under the condition of VA=12.7V, in 1% aqueous solution of nitric acid with 300 coulombs/dm
2anode the time electric weight it is carried out to the processing of electrolytic surface roughening.Measure its surfaceness, it is 0.6u m (Ra means).
Then impregnated in 30% H
2sO
4in aqueous solution, carry out 2 minutes crude removals under 55 ℃ after, at 33 ℃, 20%H
2sO
4in aqueous solution, on the face of graining, configure negative electrode, at current density 5A/dm
2under, carrying out anodic oxidation in 50 seconds, thickness is 2.7g/m
2.In addition, now the anodic oxide coating at the back side is about 0.5g/m at the central portion of aluminium plate
2, in end, be about 1.0g/m
2.
Following primary coat is mixed with coating composition, stir under 30 ℃.Approximately, after 5 minutes, find heating, after reacting 60 minutes, content is transferred in other container, by adding again 10000 weight portion methyl alcohol, modulation primary coat coating.
(2) primary coat liquid composition
Methyl alcohol 100 weight portions
Water 120 weight portions
Phosphoric acid (85% aqueous solution) 10 weight portions
3～methacryloxypropyl triethoxysilane, 25 weight portions
This aqueous coating is applied on the aluminium plate of above-mentioned processing and reaches 0.1g/m
2, carry out drying until the aluminium temperature reaches 70 ℃, then carry out cooling until aluminium temperature and reach below 50 ℃.
(3) alkali soluble resins layer
DMF (DMF) 6 weight portions
Water 2 weight portions
Ethyl cellosolve 25 weight portions
Acryl resin (1) 1.5 weight portion
The blue 603(of oil Beijing Chemical Plant) 0.07 weight portion
BYK-307 polyethoxylated dimethyl silicone copolymer
(BYK Chemie, Wallingford, CT, USA) 0.0035 weight portion
The structure of acryl resin (1) is as follows:
This aqueous coating is applied on the aluminium plate of above-mentioned processing and reaches 0.8g/m
2, carry out drying until the aluminium temperature reaches 120 ℃, then carry out cooling until aluminium temperature and reach below 50 ℃.
On the alkali soluble resins coating obtained like this, be coated with the positive-type photosensitive composition of following composition, make drying coated weight reach 1.2g/m
2, carry out drying until the aluminium temperature reaches 120 ℃, then carry out cooling until aluminium temperature and reach below 50 ℃.
(3) photosensitive layer coating liquid composition
Linear phenolic resin BTB-24 (Tian Cheng chemical plant, Weihai) 5.2 weight portions
1,2,3,-thrihydroxy-benzene condensation acetone resin PA-O (The Second Film Factory of Lucky Group) 1 weight portion
Photosensitizer P-3000 2.5 weight portions
(2.1.5 diazonium naphthoquinone sulphonate compounds, The Second Film Factory of Lucky Group)
Triazine B (The Second Film Factory of Lucky Group) 0.4 weight portion
Blue 603 (Beijing Chemical Plant) 0.5 weight portion of oil
Fluorine is surfactant FC-4432 (3M company) 0.03 weight portion
Ethyl cellosolve 100 weight portions.
Embodiment 2
Adopt method similarly to Example 1 to manufacture positive-working lithographic printing plate, difference is alkali soluble resin layer coating fluid composition difference, alkali soluble resins layer composed as follows:
DMF (DMF) 6 weight portions
Water 2 weight portions
Ethyl cellosolve 25 weight portions
PVB modified resin (Diversitec corporation, DT-5) 1.5 weight portions
The blue 603(of oil Beijing Chemical Plant) 0.07 weight portion
BYK-307 polyethoxylated dimethyl silicone copolymer
(BYK Chemie, Wallingford, CT, USA) 0.0035 weight portion
The structural formula of DT-5 is as follows:
Embodiment 3
Adopt method similarly to Example 1 to manufacture positive-type type lithographic plate, difference is alkali soluble resin layer coating fluid composition difference, alkali soluble resins layer composed as follows:
DMF (DMF) 6 weight portions
Water 2 weight portions
Ethyl cellosolve 25 weight portions
Linear phenolic resin BTB29 resin (sky, Weihai becomes chemical industry company limited) 1.3 weight portions
Tertiary butyl phenol phenolics (SP-1077, the second photographic film plant) 0.3 weight portion
Urethane resin 5715(U.S. promise reputation company) 0.5 weight portion
The blue 603(of oil Beijing Chemical Plant) 0.07 weight portion
BYK-307 polyethoxylated dimethyl silicone copolymer
(BYK Chemie, Wallingford, CT, USA) 0.0035 weight portion.
Embodiment 4
Adopt method similarly to Example 1 to manufacture positive-type type lithographic plate, difference is alkali soluble resin layer coating fluid composition difference, alkali soluble resins layer composed as follows:
DMF (DMF) 6 weight portions
Water 2 weight portions
Ethyl cellosolve 25 weight portions
CAB cellulose acetate succinate (EASTMAN company) 1.5 weight portions
The blue 603(of oil Beijing Chemical Plant) 0.07 weight portion
BYK-307 polyethoxylated dimethyl silicone copolymer
(BYK Chemie, Wallingford, CT, USA) 0.0035 weight portion.
Embodiment 5
Adopt method similarly to Example 1 to manufacture positive-type type lithographic plate, difference is photosensitive layer coating liquid composition difference, photographic layer composed as follows:
Linear phenolic resin BTB-24 (Tian Cheng chemical plant, Weihai) 5.2 weight portions
1,2,3,-thrihydroxy-benzene condensation acetone resin PA-O (The Second Film Factory of Lucky Group) 1.0 weight portions
Photosensitizer P-3000 (The Second Film Factory of Lucky Group) 1.5 weight portions
(2.1.5 diazonium naphthoquinone sulphonate compounds, The Second Film Factory of Lucky Group)
Photosensitizer PAC-NF 1.0 weight portions
(2.1.4 diazonium naphthoquinone sulphonate compounds, Tian Cheng chemical plant, Weihai)
Triazine B (The Second Film Factory of Lucky Group) 0.4 weight portion
Blue 603 (Beijing Chemical Plant) 0.5 weight portion of oil
Fluorine is surfactant FC-4432 (3M company) 0.03 weight portion
Ethyl cellosolve 100 weight portions.
Embodiment 6
Adopt method similarly to Example 1 to manufacture positive-type type lithographic plate, difference is photosensitive layer coating liquid composition difference, photographic layer composed as follows:
Linear phenolic resin BTB-24 (Tian Cheng chemical plant, Weihai) 5.2 weight portions
Linear phenolic resin BTB-29 (Tian Cheng chemical plant, Weihai) 0.5 weight portion
1,2,3,-thrihydroxy-benzene condensation acetone resin PA-O (The Second Film Factory of Lucky Group) 1 weight portion
Photosensitizer P-3000 (The Second Film Factory of Lucky Group) 2.0 weight portions
(2.1.5 diazonium naphthoquinone sulphonate compounds, The Second Film Factory of Lucky Group)
Triazine B (The Second Film Factory of Lucky Group) 0.4 weight portion
Blue 603 (Beijing Chemical Plant) 0.5 weight portion of oil
Fluorine is surfactant FC-4432 (3M company) 0.03 weight portion
Ethyl cellosolve 100 weight portions.
Comparative example 1
In comparative example 1, adopt method similarly to Example 1 to be coated with front processing to aluminum substrate, and direct photosensitive coated layer, obtain positive-working lithographic printing plate.The drying coated weight of photographic layer reaches 2.0g/m
2, carry out drying until the aluminium temperature reaches 120 ℃, then carry out cooling until aluminium temperature and reach below 50 ℃.
The photosensitive layer coating liquid composition
Linear phenolic resin BTB-24 (Tian Cheng chemical plant, Weihai) 5.2 weight portions
1,2,3,-thrihydroxy-benzene condensation acetone resin PA-O (The Second Film Factory of Lucky Group) 1 weight portion
Photosensitizer P-3000 (The Second Film Factory of Lucky Group) 1.8 weight portions
(2.1.5 diazonium naphthoquinone sulphonate compounds, The Second Film Factory of Lucky Group)
Triazine B (The Second Film Factory of Lucky Group) 0.4 weight portion
Blue 603 (Beijing Chemical Plant) 0.5 weight portion of oil
Fluorine is surfactant FC-4432 (3M company) 0.03 weight portion
Ethyl cellosolve 100 weight portions.
Comparative example 2
In comparative example 2, adopt method similarly to Example 1 to be coated with front processing to aluminum substrate, and direct photosensitive coated layer, obtain positive-working lithographic printing plate.The drying coated weight of photographic layer reaches 2.0g/m
2, carry out drying until the aluminium temperature reaches 120 ℃, then carry out cooling until aluminium temperature and reach below 50 ℃.
The photosensitive layer coating liquid composition
Linear phenolic resin BTB-24 (Tian Cheng chemical plant, Weihai) 4.2 weight portions
Tertiary butyl phenol phenolics (SP-1077, the second photographic film plant) 1.0 weight portions
1,2,3,-thrihydroxy-benzene condensation acetone resin PA-O (The Second Film Factory of Lucky Group) 1.0 weight portions
Photosensitizer P-3000 (The Second Film Factory of Lucky Group) 1.6 weight portions
(2.1.5 diazonium naphthoquinone sulphonate compounds, The Second Film Factory of Lucky Group)
Triazine B (The Second Film Factory of Lucky Group) 0.4 weight portion
Blue 603 (Beijing Chemical Plant) 0.5 weight portion of oil
Fluorine is surfactant FC-4432 (3M company) 0.03 weight portion
Ethyl cellosolve 100 weight portions.
Method of testing
(1) solvent resistance detection method
The plate obtained through said method, cut into the test-strips of 10cm*40cm, carry out the drop experiment with mixed solvent, mixed solvent forms ethylene glycol monobutyl ether: isopropyl alcohol: methyl isopropyl Ketone=20:60:20, drip on test-strips and stop 30s with dropper, after washing and drying, with Ai Seli 528 type Density Measuring Instruments, measure drop place density value.Density is less, and density loss is larger, and solvent resistance is poorer.
(2) light sensitivity test
The above-mentioned plate use thunder UV-CTP of section platemaking machine (UVP2616X) plate-making, light source is the 405nm semiconductor laser, drum type, rotating speed 900rpm.From laser energy 25mw, increase progressively the 5mw exposure, the maximum laser energy is 90mw.Rear use (prosperous prosperous 32CDN developing machine) is developed, and developer solution adds water 1:4 dilution for " Hua Guang " PD-1 type (The Second Film Factory of Lucky Group), and 23 ℃ were developed for 30 seconds.When plain net is actual while being output as 50 ± 0.5%, laser energy used is the proper exposure energy, represents light sensitivity with laser energy herein, and the larger light sensitivity of numerical value is lower, and the less light sensitivity of numerical value is higher.
(3) development latitude detects:
On UV-CTP platemaking machine (UVP2616X) platemaking machine, the exposure of 1.3 times according to the value of optimum exposure obtained above is exposed, after with different development times develop under 23 ℃ (selecting 10s, 20s, 30s, 40s here), under this condition, (blank space is not kept on file, density OD value<0.29 can to make plate reach request for utilization; Coating does not subtract film, density OD value on the spot > 1.43; The mxm. of development time site reduction 3-99%) and the difference of minimum are the development latitude of this plate.
(4) resolving power determination
By UV-CTP platemaking machine (UVP2616X) system, device resolution 2540dpi is to the space of a whole page exposed (making 1-4 pixel negative line and land).With prosperous prosperous 32CDN automatic processing machine, developed.Developer solution adds water 1:4 dilution for " Hua Guang " PD-1 type (The Second Film Factory of Lucky Group), and 23 ℃ were developed for 30 seconds.Reduce with the negative line land resolution that means plate, pixel count is less represents that resolution is higher simultaneously.
(5) press resistance rate is measured
Expose under suitable energy and develop, plate is exposed and develops and process and use magnificent light PG-1 type protection glue (the second photographic film plant) to carry out the sealing processing to the space of a whole page.After plate is placed in to J4104D type sheet printing machine (Jing Dezhen printing apparatus), print test (fountain solution Wei Gela, Hang Hua printing ink).After printing 20000 prints, the abrasion condition of the space of a whole page 50% site before and after the contrast printing (using ICPLATE forme measuring instrument Test Network dot density), wearing and tearing littlely represents that press resistance rate is higher.
According to the said determination method, measure the impact of performance of positive image UV-CTP lithographic plate plate of the present invention in Table 1.
Claims (7)
1. a positive image UV-CTP lithographic plate plate, comprise the plate support, it is characterized in that: be coated with the alkali soluble resins layer on support, be coated with the positive-type photosensitive layer on the alkali soluble resins layer, described alkali soluble resins layer contains alkali soluble resins, adds resin and illuminating colour;
Described alkali soluble resins adopts any one or more in the organic high molecular polymer of in buck or water solubility or swellability, weight average molecular weight range is between 1000-1000000, and the quality percentage composition of alkali soluble resins in the alkali soluble resins layer is 40-90%;
Described interpolation resin is polyurethane polymer, vinyl addition polymer, esters of acrylic acid addition polymer, acetals polymkeric substance or cellulosic polymer, and adding the quality percentage composition of resin in the alkali soluble resins layer is 10-60%.
2. positive image UV-CTP lithographic plate plate according to claim 1, it is characterized in that: described alkali soluble resins layer coating weight is 0.5 ~ 1.5g/m
2.
3. positive image UV-CTP lithographic plate plate according to claim 1 is characterized in that: described photographic layer comprises film-forming resin, adds resin, Photoactive compounds, light produce acid source and illuminating colour.
4. positive image UV-CTP lithographic plate plate according to claim 3, it is characterized in that: described film-forming resin is linear phenolic resin, weight-average molecular weight is 2000-10000, M
w/ M
nfor 1.5-20, the quality percentage composition of film-forming resin in photographic layer is 20-80%.
5. positive image UV-CTP lithographic plate plate according to claim 3, it is characterized in that: described interpolation resin is one or more in polyurethane polymer, vinyl addition polymer, esters of acrylic acid addition polymer, acetals polymkeric substance, cellulosic polymer, and adding the quality percentage composition of resin in photographic layer is 2-10%.
6. positive image UV-CTP lithographic plate plate according to claim 3, it is characterized in that: described Photoactive compounds is the diazonium naphthoquinone sulphonate compounds, its esterification parent is low molecule polyhydric phenols or linear phenolic resin, and the weight-average molecular weight of esterification parent is 2000-10000; M
w/ M
nfor 1.5-20, the hydroxy ester rate is the 10-80% of initial hydroxyl, the quality percentage composition 10-40% of Photoactive compounds in photographic layer.
7. positive image UV-CTP lithographic plate plate according to claim 3, it is characterized in that: described light produce acid source near ultraviolet band and ultraviolet region the compound of photolysis reactions can occur smoothly, the spectrum induction range is 350-420nm, light produce acid source in photographic layer the quality percentage composition be the 0.1-5 % by weight; Described illuminating colour is Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet or methylene blue, and the quality percentage composition of illuminating colour in the alkali soluble resins layer is 0.5-5%.
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| CN104742492B (en) * | 2013-12-30 | 2017-11-21 | 乐凯华光印刷科技有限公司 | A kind of double coating positive-printing heat-sensitive CTP plate materials |
| CN105652592B (en) * | 2014-11-13 | 2020-02-21 | 乐凯华光印刷科技有限公司 | Photosensitive composition of urethane-modified phenolic resin |
| CN104503204A (en) * | 2014-12-15 | 2015-04-08 | 山东本元功能材料有限公司 | Positive-image PS-version and CTcP lithographic plate printing plate material |
| EP3287551A4 (en) * | 2015-04-22 | 2018-10-03 | Nissan Chemical Corporation | Photosensitive fibers and method for forming fiber pattern |
| CN108219058B (en) * | 2016-12-14 | 2021-10-15 | 乐凯华光印刷科技有限公司 | UV-resistant ink positive UV-CTP lithographic printing plate material |
| CN108227384A (en) * | 2016-12-14 | 2018-06-29 | 乐凯华光印刷科技有限公司 | Negative type heat-sensitive CTP plate precursor with double-layer structure |
| WO2018133214A1 (en) * | 2017-01-20 | 2018-07-26 | 中国科学院化学研究所 | Modified phenol-aldehyde resin and synthesis method therefor, hydrophilic plate for printing and use thereof, and printing plate |
| CN110719847B (en) * | 2017-05-31 | 2021-08-31 | 富士胶片株式会社 | Lithographic printing plate precursor and method for producing lithographic printing plate |
| CN109799681B (en) * | 2019-01-29 | 2022-05-20 | 浙江康尔达新材料股份有限公司 | Ultraviolet and visible light sensitive positive working lithographic printing plate precursor and method for forming image |
| CN110187605A (en) * | 2019-05-23 | 2019-08-30 | 海宁市速美工贸有限公司 | Coating is imaged in heat-sensitive CTP plate |
| CN113954502B (en) * | 2021-10-26 | 2023-04-07 | 浙江康尔达新材料股份有限公司 | Photosensitive negative-working lithographic printing plate precursor and method for making lithographic printing plate by using the same |
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