WO2016095636A1 - 一种阳图型PS版和CTcP平版印刷版版材 - Google Patents

一种阳图型PS版和CTcP平版印刷版版材 Download PDF

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Publication number
WO2016095636A1
WO2016095636A1 PCT/CN2015/094577 CN2015094577W WO2016095636A1 WO 2016095636 A1 WO2016095636 A1 WO 2016095636A1 CN 2015094577 W CN2015094577 W CN 2015094577W WO 2016095636 A1 WO2016095636 A1 WO 2016095636A1
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Prior art keywords
plate
ctcp
photosensitive
mass
compound
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PCT/CN2015/094577
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English (en)
French (fr)
Inventor
刘扬
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青岛蓝帆新材料有限公司
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Priority to EP15869145.1A priority Critical patent/EP3236315B1/en
Publication of WO2016095636A1 publication Critical patent/WO2016095636A1/zh

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

Definitions

  • the invention belongs to the field of printing plate making, and in particular relates to a positive image PS plate and a CTcP lithographic printing plate plate used in lithographic printing.
  • the invention of the diazonaphthene-based positive-image PS plate by Kalle in Germany in the 1930s has been more than 80 years old.
  • This system has been the basic system of the commercial positive-image PS plate, diazonaphthoquinone sulfonate.
  • a photosensitive compound a novolac resin is used as a film-forming resin, a photosensitive compound and a film-forming resin are mixed in a certain ratio, a certain amount of a background coloring dye is added, and a positive electrode PS plate photosensitive liquid is prepared by using a solvent such as ethylene glycol monoalkyl ether.
  • the photosensitive compound diazonaphthoquinone sulfonate compound in the photosensitive layer of the plate is sensitive to ultraviolet light, and the diazo group is decomposed by ultraviolet light irradiation, and the anthracene azide compound forms an indolinone, and then converted into tannic acid, so that when used
  • the alkaline developing solution is developed, the light-receiving portion of the plate material is dissolved and removed to expose the hydrophilic aluminum plate base, exhibiting hydrophilicity, and becomes a non-image portion which is hydrophilic during printing;
  • the ortho-azide azide is intermolecularly associated with the phenolic hydroxyl group on the film-forming phenolic resin to form a stable six-ring structure, thereby enhancing the alkali-solubility of the coating and not in the development time.
  • the traditional positive image PS version is also rapidly developed for computer-to-plate CTcP technology.
  • This technology uses a common high-pressure mercury lamp source and / or 405nm UV laser source for computer-to-plate, to improve the plate quality and efficiency, and to the plate.
  • the requirements for degree, resolution and printing durability are high.
  • Traditional PS The version should be adapted to the requirements of laser plate making, and the sensitivity is the most critical factor. In order to meet the challenges of CTP technology, major companies have improved their extensive research in improving the performance of positive PS.
  • JP2005352004, JP2003043683 there are many patents for improving sensitivity and resolution at the same time, JP2003195501, JP2001138652, JP2001066773, JP9319077, US6010820, etc., the above patents add a carboxyl group-containing fluorine-containing acrylic copolymer by adjusting the ratio of photosensitive resin.
  • a development accelerator such as a cresol resin or an acid anhydride compound adopts a double coating structure in combination with a chemical amplification (acid proliferation) mechanism to improve the sensitivity of the plate material, thereby realizing computer direct plate making.
  • the sensitivity and alkali-resistant water that is, after a short exposure of the photosensitive coating, the exposed portion can be completely dissolved in the developer, and the non-exposed portion has as little loss as possible.
  • This balanced solution is limited.
  • both the conventional PS version and the CTcP version have problems of poor chemical resistance, and the solvent resistance is not good in low printing durability, poor chemical cleaning agent, UV resistant ink, etc., if the above performance is to be improved.
  • the baking operation is adopted, and the baking operation requires problems such as high temperature baking, inability to repair the plate, and poor precision. As the national environmental protection requirements become more and more strict, the VOC emissions of the printing factory are gradually strictly controlled, and there is no VOC.
  • the technical problem to be solved by the invention is to improve the chemical resistance of the positive image PS plate and the CTcP plate material, and at the same time improve the sensitivity, resolution and printing durability of the plate material, so that the plate material is suitable for UV ink printing.
  • a positive PS plate and a CTcP lithographic printing plate of the present invention comprise a hydrophilic layer coated with a bottom layer composed of a photosensitive composition coated with a photosensitive layer a top layer composed of the composition, the top layer has a weight of 0.2 to 1.0 g/m 2 , and the photosensitive layer coating has a weight of 0.5 to 1.5 g/m 2 , and the bottom layer and the top layer are sensitive to visible light and ultraviolet light, and may be exposed after exposure. It is alkali-soluble, exposed to visible light and/or ultraviolet light, and after being subjected to an alkaline solution development treatment, the exposed region is dissolved and removed, and the non-exposed region is insoluble or slightly dissolved and retained.
  • the underlayer includes a positive-type photosensitive layer composed mainly of a chemical resistant functional resin, a photosensitive compound, a development accelerator, and a background coloring dye.
  • the chemical resistant functional resin of the bottom layer is a copolymer represented by Formula I, wherein the copolymer has one of a benzylsulfonylaminoacrylamide and an N-arylmaleimide cyclic unit on a branched carbon atom. Or a molecular weight of the copolymer is between 1000 and 100000; the structural unit of the benzylsulfonamide acrylamide monomer accounts for 5% to 70% by mass of the copolymer, and the N-aryl The mass fraction of the copolymer of the quinolamide structural unit is 5% to 70%; the mass percentage of the chemical resistant functional resin in the underlying photosensitive composition is 75-85%;
  • R represents one of H, C1 to C4 alkyl or aryl
  • R1, R2 and R3 represent H or CH3
  • v, w, x, y, and z represent each monomer component in the copolymer molecule, respectively.
  • the mass fraction is 5% to 70%; the sum of the mass fractions of the v, w, x, y, and z components is 100%.
  • the photosensitive compound of the underlayer is a 1,2-naphthoquinone-2diazo-4-sulfonate compound or a 1,2-naphthoquinone-2diazo-5-sulfonate compound
  • the esterification precursor of the sulfonate compound is a low molecular polyhydric phenol compound, a pyrogallol-acetone polycondensate and/or a novolac resin, and the esterified precursor has a weight average molecular weight of 50 to 20,000; Mw/Mn is 1.5 to 20, the hydroxyl esterification rate is the initial hydroxyl group 10% to 80%, the mass fraction of the photosensitive material in the underlying photosensitive layer is 2% to 20%.
  • the developing accelerator of the underlayer is a mixture of a carboxylic acid, a carboxylic anhydride, a sulfonic acid and a phosphoric acid compound in an amount of from 3% to 10% by mass based on the mass of the underlying photosensitive composition.
  • the background coloring dye of the bottom layer is a mixture of one or more of Victoria Pure Blue, Basic Brilliant Blue, Oil Blue, Crystal Violet, Ethyl Violet, Methyl Violet or Methylene Blue, the coloring dye
  • the mass percentage in the top photosensitive composition is 1% to 3%, respectively.
  • the top layer composition includes a film-forming resin, a photosensitive compound, a photoacid generator, and a background coloring dye.
  • the film-forming resin of the top layer is a novolac resin having a weight average molecular weight of 2,000 to 20,000 and a Mw/Mn of 1.5 to 20, and the mass percentage of the film-forming resin in the top photosensitive composition is 53.5%. ⁇ 65%.
  • the photosensitive compound of the top layer is a 1,2-naphthoquinone-2diazo-4-sulfonate compound or a 1,2-naphthoquinone-2diazo-5-sulfonate compound, and an ester thereof
  • the precursor is a low molecular polyphenol compound, a pyrogallol-acetone polycondensate and/or a novolac resin.
  • the esterified precursor has a weight average molecular weight of 50-20000; Mw/Mn is 1.5-20, and the hydroxyl esterification rate is 10% to 80% of the initial hydroxyl group, the mass percentage of the photosensitive material in the top photosensitive layer is 30% to 40%.
  • the development accelerator of the top layer is a mixture of a carboxylic acid, a carboxylic anhydride, a sulfonic acid and a phosphoric acid compound in an amount of from 1% to 5% by mass based on the mass of the top photosensitive composition.
  • the coloring dye of the top layer is a mixture of one or more of Victoria Blue, Basic Blue, Oil Blue, Crystal Violet, Ethyl Violet, Methyl Violet or Methylene Blue, and the coloring dye is photosensitive on the top layer.
  • the mass percentage in the layer is from 0.1% to 1%.
  • the photoacid generator is a compound which can undergo photodecomposition reaction in the near ultraviolet region and the ultraviolet region, and the spectral sensing range is 350 to 420 nm, and the photoacid generator is in the quality of the top photosensitive composition.
  • the percentage by weight is from 0.1% to 0.5%.
  • the photosensitive composition is composed as follows:
  • the chemical resistant copolymer of the present invention is an acrylic resin containing a benzylsulfonamide acrylamide on a branched carbon atom, and further is a monomer compound of the formula II and acrylic acid or methacrylic acid, acrylate or methacrylate, benzene.
  • a copolymer of a monomer such as an ethylene group, a hydroxyl group-containing methacrylate or an N-substituted maleimide, wherein R4 is H, an alkyl group or a substituted alkyl group; and R5 is H, C1 to C6.
  • Alkyl, aryl or vinyl or propenyl; other comonomers are one or a combination of the following:
  • a fatty hydroxy acrylate and methacrylic acid acrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate.
  • alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, decyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate.
  • alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, benzyl methacrylate
  • alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, benzyl methacrylate
  • alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, benzyl methacrylate
  • 2-chloroethyl methacrylate 2-chloroethyl methacrylate
  • cyclohexyl methacrylate polyethylene glycol
  • Acrylamide and methacrylamide such as: acrylamide, methacrylamide, N-methoxyacrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide N-phenylacrylamide, N-nitrophenylacrylamide, N-vinylamide, N-carboxyphenylmethacrylamide or N-phenyl N-ethylacrylamide.
  • a vinyl ether such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, mercapto vinyl ether or phenyl vinyl ether.
  • Vinyl esters such as vinyl acetate, vinyl acetate, vinyl butyrate or vinyl benzoate.
  • Styrene such as styrene, 1-methylstyrene, methylstyrene or chloromethylstyrene.
  • a ketene such as methyl ketene, ethyl ketene, propyl vinyl ether or phenyl vinyl ether.
  • Ethylene such as ethylene, propylene, urea-containing side chain, butene, isobutylene or isopropylene.
  • An unsaturated imide such as N-maleimide, N-acrylimide, N-ethylmethacrylamide or N-propylmethacrylamide.
  • An unsaturated carboxylic acid such as acrylic acid, methacrylic acid maleic anhydride or itaconic acid.
  • the molecular weight of the chemically resistant functional resin is between 1000 and 100000, and the structural unit of the benzylsulfonamide acrylamide monomer accounts for 5% to 70% by mass of the copolymer, and the N-aryl Malay
  • the mass fraction of the copolymer of the imide structural unit is 5% to 70%; and the mass percentage of the chemical resistant functional resin in the underlying photosensitive composition is 75% to 85%.
  • the film-forming resin is a novolac resin
  • the novolac resin is phenol, m-cresol, o-cresol, p-cresol, phenol and m-cresol having a molar ratio of 3:7 to 7:3, M-cresol and p-cresol, m-, o-cresol, 2, 4 molar ratio of 3:1 to 1.5:1 phenol and tert-butylphenol, molar ratio of 9:1 to 5:5
  • xylenol, 3,5-xylenol, N-phenylmaleimide modified m-/p-mixed cresol A phenolic phenolic resin obtained by polycondensing phenols and formaldehyde in different proportions; the weight average molecular weight thereof is 2,000 to 20,000 or 2,000 to 10,000 or 2,500 to 7,500, and the Mw/Mn is 1.5 to 20 or 1.5 to 10.
  • the molecular weight is more than 20,000, the linearity of the phenolic resin decreases, the degree of branching increases, so that the solubility in the alkali developing solution decreases, and the development encounters difficulty; the molecular weight is too small, the alkali resistance is too weak during development, and photobleaching is apt to occur.
  • Membrane phenomenon the printing durability of the plate is weak, which also affects the resolution of the plate and the reduction of the dot.
  • the amount of the film-forming resin added is 53.5% to 65% by mass based on the total weight of the top photosensitive composition.
  • the photosensitive compound in the photosensitive member of the positive image PS plate and the CTcP plate of the present invention is a diazonaphthoquinone sulfonate compound, and the esterification precursor thereof may be a low molecular polyphenol compound or a linear phenol resin. Molecular compound.
  • one or two of 1,2-naphthoquinone-2diazo-5-sulfonate compounds, and the two types of sulfonate esters may be used singly or in combination to ensure a high sensitivity of the plate material.
  • the combination ratio of the two photosensitive compounds is 0.2:1 to 1:0.2 or 0.5:1 to 1:0.5.
  • the esterification precursor of the sulfonate compound is a low molecular polyphenol compound, a pyrogallol-acetone polycondensate and/or a novolac resin, and the esterified precursor has a weight average molecular weight of 50 to 20000; Mw/ The Mn is from 1.5 to 20, the hydroxyl esterification rate is from 10% to 80% of the initial hydroxyl group, and the mass fraction of the photosensitive material in the top photosensitive layer is from 30% to 40%.
  • the amount of photosensitizer is too large, the solubility is too strong, the development is difficult, the sensitivity is low, the resolution is also decreased; the amount of photosensitizer is too small, the solubility is insufficient, the alkali resistance is poor, the photo-release phenomenon is easy to occur, and the printing of the plate is resistant. The force is low.
  • the photoacid generator used in the invention can be smoothly developed in the near ultraviolet region and the ultraviolet region (320 to 450 nm).
  • the best spectral sensing range of the compound for photodegradation is 350-420 nm.
  • a representative trichloromethyltriazine compound such as 1-phenyl-3,5-bistrichloromethyltriazine, 1-methoxyphenyl-3,5-bistrichloromethyltriazine, L-p-methoxystyryl-3,5-bistrichloromethyltriazine, 1-methoxyphenyl-3,5-bistrichloromethyltriazine, and the like.
  • the photoacid generator is used in an amount of from 0.1 to 0.5% by weight based on the total mass of the photosensitive composition.
  • the background coloring dye used in the present invention is a mixture of one or more of Victoria Pure Blue, Basic Brilliant Blue, Oil Blue, Crystal Violet, Ethyl Violet, Methyl Violet or Methylene Blue, in view of absorption of ultraviolet rays.
  • the plate sensitivity is lowered, preferably Victoria Pure Blue, Basic Brilliant Blue, Oil Dissolved Blue, and the coloring dye is 1% to 3% by mass in the photosensitive layer.
  • Other added resins may also be polyurethane, acetal resin, acrylic resin, etc.
  • the development accelerator is a mixture of one or more of a carboxylic acid, a carboxylic anhydride, a sulfonic acid, and a phosphoric acid compound, preferably citric acid, tartaric acid, maleic acid, benzoic acid, phthalic acid, hydroxybenzoic acid, dihydroxybenzene. Any one or more of formic acid, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride triazole, and the like.
  • the support used in the present invention may be dimensionally stable aluminum or an alloy thereof (e.g., an alloy with silicon, copper, manganese, magnesium, chromium, zinc, lead, secret, nickel).
  • the aluminum plate may be an aluminum plate manufactured by a usual semi-continuous casting method (DC method), or may be an aluminum plate manufactured by a continuous casting calendering method.
  • DC method semi-continuous casting method
  • a twin roll method, a belt casting method, a block casting method, or the like can be used.
  • the content of the dissimilar elements in the alloy is 10% by weight or less.
  • the thickness of the aluminum plate is preferably about 0.1 mm to 0.6 mm. Further, a plastic film or paper in which aluminum or aluminum alloy is laminated or vapor-deposited may also be used.
  • the support is an aluminum plate
  • various treatments are usually applied to the surface thereof depending on the purpose.
  • the aluminum surface is first cleaned by degreasing or electrolytic grinding treatment and decontamination treatment of the aluminum plate. Then, a mechanical surface roughening treatment or/and an electrochemical surface roughening treatment is performed to impart fine irregularities on the surface of the aluminum plate. In addition, chemical etching treatment and decontamination treatment are sometimes added. Then, in order to increase the abrasion resistance of the surface of the aluminum plate, an anodizing treatment is performed, and then the aluminum surface is subjected to a hydrophilization treatment or/and a sealing treatment as needed.
  • the overflow waste liquid of the electrolytic solution used in the electrochemical surface roughening treatment can be used as the decontamination treatment liquid, but at this time, the water washing treatment after the decontamination treatment can be omitted.
  • the first step degreasing and electrolytic grinding
  • the rolling oil, the natural oxide film, the dirt, and the like which are present on the aluminum plate are removed to uniformly perform electrochemical surface roughening, and the aluminum plate is electrolytically ground in an acidic aqueous solution or in an acid or alkali aqueous solution. A chemical etching process of the aluminum plate was performed.
  • the second step electrolytic grinding
  • a known aqueous solution for electrolytic polishing can be used.
  • An aqueous solution mainly composed of sulfuric acid or phosphoric acid is preferred, and an aqueous solution mainly composed of phosphoric acid is particularly preferred.
  • the current can be DC, pulsed DC, or AC, but continuous DC is preferred.
  • the electrolytic treatment apparatus a known apparatus for electrolytic treatment such as a flat tank or a star tank can be used.
  • the third step chemical etching treatment in an acid or alkali aqueous solution
  • the liquid temperature is preferably 25 to 90 ° C, and preferably 1 to 120 seconds.
  • the concentration of the acidic aqueous solution is preferably from 0.5% to 25% by mass.
  • the etching treatment when chemical etching is performed using an aqueous solution of an alkali, since dirt is formed on the surface of aluminum, it is generally carried out by using phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid of two or more kinds of acids including these.
  • Decontamination treatment The acidic aqueous solution used can be dissolved in 0 to 5% by weight of aluminum, and the liquid temperature is from room temperature to 70 ° C, and the treatment time is preferably from 1 to 30 seconds. Further, as the acidic aqueous solution, a waste liquid of an electrolytic solution used for electrochemical surface roughening treatment or the like can be used, and care must be taken not to dry the aluminum plate and analyze it in the decontamination liquid.
  • the brush granulation treatment is excellent as a large amount of continuous treatment.
  • a slurry of silica sand, aluminum hydroxide or the like is sprayed on the surface of the aluminum plate, and a nylon brush roll having a brush diameter of 0.2 to 0.9 mm is rotated at 50,500 rpm to carry out a mechanical surface roughening treatment.
  • the rotation of the pressing force of the brush drives the power consumption of the motor (the substantial power of the mechanical loss of the drive motor is removed).
  • it is 0.2 to 15 kW.
  • Step 6 Electrochemical surface roughening treatment
  • An aqueous solution mainly using hydrochloric acid or nitric acid using a DC electrochemical surface roughening treatment which can be used in an electrochemical surface roughening treatment using a usual alternating current, can be used in a hydrochloric acid or nitric acid aqueous solution of 1 to 100 g/L.
  • hydrochloric acid or a nitric acid compound having hydrochloric acid ions such as saturated aluminum nitrate, sodium nitrate or nitric acid is added in an amount of 1 g/L.
  • Step 7 Chemical etching treatment using acid-alkaline solution
  • the chemical etching treatment is performed for the purpose of removing the entire surface of the sand hole of the fine unevenness formed in the mechanical surface roughening treatment or the electrochemical surface roughening treatment, dirt, and the like.
  • the liquid temperature is preferably 25 to 90 ° C.
  • the treatment is carried out for 1 to 120 seconds.
  • the concentration of the acidic aqueous solution is preferably 0.5 to 25% by weight, and more preferably 0.5 to 5% by weight of aluminum dissolved in the acidic aqueous solution.
  • the concentration of the aqueous alkali solution is preferably 5 to 30% by weight, and more preferably 1 to 30% by weight of aluminum dissolved in the aqueous alkali solution.
  • Step 8 Anodizing
  • anodizing treatment is performed.
  • the electrolyte used in the anodizing treatment of the aluminum plate if a porous oxide film is formed, any electrolyte can be used. Sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixture thereof is usually used. The concentration of these electrolytes is appropriately determined depending on the kind of the electrolyte.
  • the treatment conditions for anodization vary depending on the electrolyte used, and therefore cannot be generalized.
  • the amount of the anodized film is preferably 1.0 g/m 2 or more, and more preferably in the range of 2.0 to 6.0 g/m 2 .
  • the aluminum surface is subjected to a hydrophilization treatment as needed.
  • the support is immersed in an aqueous solution of sodium silicate or subjected to electrolytic treatment.
  • water washing, sealing After the completion of each treatment, in order to prevent the treatment liquid from being carried to the next step, water removal by nip roller and water washing by spraying are performed. It is preferred to carry out the sealing treatment after the anodizing treatment.
  • the plugging treatment is carried out by dipping in a hot aqueous solution containing hot water and an inorganic salt or an organic salt, and using a steam bath.
  • the photosensitive layer composition is dissolved and dispersed at a solid concentration of 2% to 20% by weight, and applied to the above-mentioned hydrophilic sand-imprinted base and dried.
  • the coating amount of the photosensitive layer is usually preferably 0.5 to 2.0 g/m 2 after drying, and as the coating amount is decreased, the amount of exposure for obtaining an image is reduced, and the film strength is lowered. As the amount of coating increases, the amount of exposure increases, and the strength of the film increases.
  • the dissolution of the photosensitive layer composition may be selected from one, two or more solvents.
  • the solvent used in this patent includes acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydroanthracene.
  • a surfactant may be added to the photosensitive layer of the positive-working lithographic printing plate.
  • the coating method of the photosensitive layer may be a method of applying a bar, an extrusion coater coating method, a rotary coating, a dip coating, an anilox coating, an air scissor coating, or a roll coating.
  • a method such as cloth, blade coating, curtain coating, or a method of a ball coater, but is not limited thereto.
  • the exposure light source for the positive-working lithographic printing plate of the present invention is a carbon arc lamp, a high-pressure mercury lamp, an ammonia lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a ⁇ laser, a hydrogen ion laser, an FD-YAG laser, ⁇ Laser laser, semiconductor laser (350 nm to 450 nm), image exposure of the photosensitive layer, image exposure using these conventionally known rays, and development treatment with an alkaline solution, that is, the plate is immersed in the developer at 0 At a temperature of ⁇ 60 ° C, preferably 15 to 40 ° C, the coating of the exposed area is dissolved in the developer by brush wiping or spraying, etc., and is removed from the aluminum plate base, and the non-exposed area is retained, so that the aluminum plate is An image is formed on the surface of the support.
  • the lithographic printing method can further include processes such as trimming and upper protective tape.
  • X-Rite 528 type density meter To measure the density at one end of the test strip, soak one end of the measured density into the test solvent, remove it after 10 minutes, dry it with a clean soft cloth, and measure the density value of the soaking area with an X-Rite 528 Densitometer. The difference in density loss is calculated, and the larger the difference, the worse the solvent resistance.
  • the plate was made with a Cory UV-CTP platesetter (UV426E3X+), the light source was a 405 nm semiconductor laser, and the outer drum was rotated at 900 rpm. Starting from a laser energy of 30 mw, the exposure is increased by 5 mw and the maximum laser energy is 70 mw. After development (Huqiu hu.q PT-125 developing machine), the developing solution was diluted with "black wood" HUV-PN series developer, diluted with water 1:4, and developed at 25 ° C for 25 seconds. When the actual output of the flat screen is 50 ⁇ 0.5%, the laser energy used is the appropriate exposure energy.
  • the laser energy is used to represent the sensitivity. The higher the value, the lower the sensitivity, and the smaller the value, the higher the sensitivity.
  • the device resolution is 2540dpi to expose the plate (making 1 to 4 pixels of Yin and Yang).
  • the developing solution was diluted with "black wood" HUV-PN series developer, diluted with water 1:4, and developed at 25 ° C for 25 seconds. Simultaneous reduction with a negative line indicates the resolution of the plate. The smaller the number of pixels, the higher the resolution.
  • the plate On the Kore UV-CTP platesetter (UV426E3X+) platesetter, exposure was performed at 1.3 times the exposure amount of the optimum exposure amount obtained above, and then developed at 23 ° C with different development times (here, 10 s, 20 s) , 30s, 40s), under this condition, the plate can be used to meet the requirements (the blank is not left, the density OD value is ⁇ 0.29; the coating is not reduced in the field, the density OD value is >1.43; the dot reduction is 3% to 99%)
  • the difference between the highest value and the lowest value of the development time is the development latitude of the plate.
  • the exposed and developed plate is cut into a sample of 8cm ⁇ 30cm size, fixed in a container with a sealable capacity of about 1000ml, and added to the formula chemical of Table 1.
  • the plate is required to contact the chemicals and rotate for 20 minutes.
  • the exposed plate is cut into a sample of 8cm ⁇ 30cm size, fixed in a container with a sealable capacity of about 1000ml, and the formulation chemicals of Table 2 are added, and the plate is required to contact the chemicals, and the rotation is kept for 20 minutes.
  • Investigate the density loss of the coating and measure the density with the X-Rite 528 Densitometer. The smaller the plate density, the greater the coating loss and the worse the printing resistance.
  • the invention has the beneficial effects of improving the solvent resistance of the positive UV-CTP plate material, improving the sensitivity, resolution, development latitude and printing durability of the plate material and being suitable for UV ink printing.
  • the invention is described below in conjunction with the examples, but the invention is not limited by the examples.
  • Ethylene is standard, GPC column: 708*300MM, detector wavelength: 220nm, Sample concentration: 1.0mg / ml, injection volume of 20ul Mobile phase: tetrahydrofuran, column temperature: 35 °C.
  • the reaction was continued within 1 hour, and the reaction was continued for 4 hours. After the reaction was completed, the temperature was lowered to room temperature, 0.5 g of hydroquinone (dissolved in 50 ml of ethyl cellosolve) was added, and the mixture was stirred for 10 minutes. Then, the reaction mixture was slowly added to 4 liters of water to obtain a white solid, which was filtered, washed three times, and dried in a vacuum drying oven to obtain an acrylic resin FSR3 containing the present invention, and the weight average molecular weight MW was passed through gel permeation chromatography (Aglilient Technologies 1120 Compact).
  • LC LC determination
  • measurement conditions are based on polystyrene, GPC column: 708*300MM, detector wavelength: 220nm, injection concentration: 1.0mg/ml, injection volume 20ul mobile phase: tetrahydrofuran, column temperature: 35 ° C.
  • the average molecular weight MW is determined by gel permeation chromatography (Aglilient Technologies 1120 Compact LC) (GPC), the measurement conditions are based on polystyrene, GPC column: 708*300 MM, detector wavelength: 220 nm, injection concentration: 1.0 mg/ml, Injection volume 20 ul mobile phase: tetrahydrofuran, column temperature: 35 ° C.
  • the base used in the examples and comparative examples was treated with a preferred aluminum plate according to the following process, and a hydrophilic surface was obtained by the following treatment.
  • the aluminum plate is subjected to decontamination treatment, and the surface is cleaned with an organic solvent, acid or alkali water, and the dissolved amount is 5-8 g/m 2 ;
  • Electrolytic sand It is required to have good lipophilicity in the graphic part of the plate, and the hydrophilicity of the blank part is good.
  • the surface of the aluminum plate has many micropores, and the purpose of sealing is to These micropores are blocked and soaked with an aqueous solution of sodium silicate to achieve the purpose of hydrophilization and sealing.
  • the obtained coating liquid was applied by spin coating onto the above-mentioned 400*510*0.27 mm substrate which was dried on a hydrophilic sand-imprinted substrate and dried. Dry in an oven at 150 ° C for 3 minutes. The appropriate rotation speed was controlled during the coating to obtain a final coating thickness of 0.9 g/m 2 . This goes to the underlying pattern D1 - D4.
  • the obtained coating liquid was applied by spin coating to the primer-coated plates D1 to D4. Dry in an oven at 120 ° C for 3 minutes. The appropriate rotation speed was controlled during the coating to obtain a final coating thickness of 0.8 g/m 2 . This goes to the underlying pattern T1 - T4.
  • the UV-CTP version of the photosensitive layer coating solution was prepared according to the following formulation:
  • the two comparative coating liquids were applied by spin coating to a 400*510*0.27 mm substrate which was passed through a hydrophilic sand-imprinted substrate and dried. Dry in an oven at 120 ° C for 3 minutes. The appropriate rotation speed was controlled during the coating to obtain a final coating thickness of 1.8 g/m 2 . This goes to the underlying pattern C1 - C2.
  • Sensitivity mv Development latitude Resolution T1 45 20 1 pixel T2 50 25 2 pixels T3 55 20 1 pixel T4 55 20 2 pixels C1 60 15 3 pixels C2 60 10 3 pixels

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Abstract

一种阳图型PS版和CTcP平版印刷版版材，版材包括一种亲水支持体，和在其上涂覆一种曝光后可碱溶的底层和顶层。底层感光组合物包括耐化学品功能树脂、光敏化合物、背景着色染料，其中，耐化学品功能树脂其支链碳原子上带有苄磺酰氨基和N-芳基马来酰亚胺循环单元，分子量在1000～100000之间。顶层感光组合物由成膜树脂、光敏化合物、光致产酸剂、背景着色染料组成，其底层和顶层对可见光和紫外光敏感，用可见光和/或紫外光曝光后，经过碱性溶液显影处理，曝光区域发生溶解而被清除，非曝光区域不溶或受到轻微溶蚀而保留。

Description

一种阳图型PS版和CTcP平版印刷版版材 技术领域
本发明属于印刷制版领域，尤其涉及一种关于平版印刷中所用的阳图PS版和CTcP平版印刷版版材。
背景技术
从20世纪30年代德国Kalle公司发明重氮萘醌系阳图PS版以来，到目前有80多年的历史，这一体系一直为商品化阳图PS版的基本体系，重氮萘醌磺酸酯作为光敏化合物，线性酚醛树脂作为成膜树脂，光敏化合物和成膜树脂以一定比例混合，加入一定量的背景着色染料，用乙二醇单烷基醚等溶剂调配成阳图PS版感光液，将其涂布于具有亲水砂目化结构的铝版基上，经干燥而得到预涂感光版PS版。版材感光层中的光敏化合物重氮萘醌磺酸酯化合物对紫外光敏感，经紫外光照射后重氮基分解，邻醌叠氮化合物生成茚酮，之后转变为茚酸，这样，当用碱性显影液显影时，版材上见光的部分被溶解而除去，露出亲水性的铝版基，表现出亲水性，在印刷时变为亲水性的非图文部分；而未曝光的部分，邻醌叠氮化合物与成膜性酚醛树脂上的酚羟基发生分子间缔合，形成稳定的六圆环结构，从而增强了涂层的抗碱溶解性，在显影时间内不会或少被碱性显影液溶解，因此版材上未曝光的部分仍然留在铝版基上，在印刷时变成亲油性的图文部分。
随着计算机、激光及信息技术的发展，除了热敏制版原理的CTP技术之外。传统阳图PS版应用于计算机直接制版的CTcP技术也得到快速发展，该技术采用普通高压汞灯光源和/或405nm紫外激光光源进行计算机直接制版，为提高制版质量和效率，对版材的感光度、分辨力和耐印力等方面要求较高。传统PS 版要适应激光制版的要求，感度满足要求是最关键的因素。为迎接CTP技术挑战，各大公司在提高阳图PS版感性能方面改进了广泛研究。如JP2005352004,JP2003043683，同时提高感光度和分辨力方面专利也不少，JP2003195501,JP2001138652,JP2001066773,JP9319077,US6010820等，上述专利通过调整感光树脂比例，添加含羧基、含氟的丙烯酸共聚物，纯间甲酚树脂，酸酐类化合物等显影促进剂，采用双涂层结构，结合使用化学增幅(酸增殖)机理等方法来提高版材的感光度，从而实现计算机直接制版。
但从传统PS版的感光成像原理出发，感光度和耐碱水性，即感光涂层在短时间的曝光后，曝光部分能彻底溶解于显影液，而非曝光部分尽量少的有损失。这种平衡的解决受到限制。而且不管是常规PS版还是CTcP版都存在耐化学品性不好的问题，耐溶剂性不好表现在耐印力低、耐化学清洗剂差，不耐UV油墨等等，如果要改善上述性能一般采取烤版操作，烤版操作存在需要高温烘烤、无法修版、精度变差等问题，随着国家对环保要求越来越严格，对于印刷厂的VOC排放也逐渐严格控制，同时无VOC排放的UV固化油墨的不断发展，除了无VOC排放的有点外，还具有色泽鲜艳、适应性好、对热敏感基材也适用等有点，因此提高版材耐溶剂型越来越重要。
发明内容
本发明要解决的技术问题是提高阳图PS版和CTcP版材的耐化学品性，同时提高了版材的感度、分辨率及耐印力，使版材适合UV油墨印刷。
为解决上述技术问题，本发明的技术方案如下：
本发明的一种阳图PS版和CTcP平版印刷版版材，包括一个亲水层，所述亲水层上涂有一个由感光组合物组成的底层，所述底层上涂有一个由感光的组合物组成的顶层，所述顶层重量为0.2～1.0g/m2，所述感光层涂层重量为0.5～ 1.5g/m2，所述底层和顶层对可见光和紫外光敏感，曝光后可碱溶，用可见光和/或紫外光曝光后，经过碱性溶液显影处理，曝光区域发生溶解而被清除，非曝光区域不溶或受到轻微溶蚀而保留。所述底层包括阳图型感光层，所述感光层主要由耐化学品功能树脂、光敏化合物、显影促进剂、背景着色染料组成。
所述底层的耐化学品功能树脂为式I表示的共聚物，所述共聚物的支链碳原子上带有苄磺酰氨基丙烯酸酰胺和N-芳基马来酰亚胺循环单元中的一种或两种；所述共聚物的分子量在1000～100000之间；所述苄磺酰胺基丙烯酸酰胺单体的结构单元所占共聚物的质量分数为5％～70％，所述N-芳基马来酰亚胺结构单元所占共聚物的质量分数为5％～70％；所述耐化学品功能树脂在底层感光组合物中的质量百分含量为75～85％；
Figure PCTCN2015094577-appb-000001
其中，R代表H、C1～C4烷基或芳基的一种；R1、R2和R3代表H或CH3；v、w、x、y、z分别代表各单体组分在共聚物分子中所占质量分数，所述质量分数为5％～70％；所述v、w、x、y、z各组分质量分数之和为100％。
进一步地，所述底层的光敏化合物是1,2-萘醌-2重氮-4-磺酸酯类化合物或1,2-萘醌-2重氮-5-磺酸酯类化合物，所述磺酸酯类化合物的酯化母体是低分子多元酚类化合物、连苯三酚-丙酮缩聚物和/或线性酚醛树脂，所述酯化母体的重均分子量为50～20000；Mw/Mn为1.5～20,羟基酯化率是最初羟基的 10％～80％，光敏物质在底层感光层中的质量分数为2％～20％。
进一步地，所述底层的显影促进剂是羧酸、羧酸酐、磺酸及磷酸类化合物的混合物，加入量为底层感光组合物质量百分含量的3％-10％。
进一步地，所述底层的背景着色染料为维多利亚纯蓝、碱性艳蓝、油溶蓝、结晶紫、乙基紫、甲基紫或亚甲基蓝中的一种或几种的混合物，所述着色染料分别在顶层感光组合物中质量百分含量为1％～3％。
进一步地，所述顶层组合物包括成膜树脂、光敏化合物、光致产酸剂、背景着色染料。
进一步地，所述顶层的成膜树脂为线性酚醛树脂，重均分子量为2000～20000,Mw/Mn为1.5～20，所述成膜树脂在顶层感光组合物中的质量百分含量为53.5％～65％。
进一步地，所述顶层的光敏化合物是1,2-萘醌-2重氮-4-磺酸酯类化合物或1,2-萘醌-2重氮-5-磺酸酯类化合物，其酯化母体是低分子多元酚类化合物、连苯三酚-丙酮缩聚物和/或线性酚醛树脂，酯化母体的重均分子量为50-20000；Mw/Mn为1.5～20,羟基酯化率是最初羟基的10％～80％，光敏物质在顶层感光层的质量百分含量为30％～40％。
进一步地，所述顶层的显影促进剂是羧酸、羧酸酐、磺酸及磷酸类化合物的混合物，加入量为顶层感光组合物中质量百分含量1％-5％。
进一步地，所述顶层的着色染料为维多利亚纯蓝、碱性艳蓝、油溶蓝、结晶紫、乙基紫、甲基紫或亚甲基蓝中的一种或几种的混合物，着色染料在顶层感光层中质量百分含量为0.1％～1％。
进一步地，所述光致产酸剂为在近紫外区及紫外区可发生光分解反应的化合物，光谱感应范围为350～420nm，所述光致产酸剂在顶层感光组合物中的质 量百分含量为0.1％～0.5％。
所述感光组合物组成如下：
1、耐化学品共聚物
本发明的耐化学品共聚物是支链碳原子上含苄磺酰胺基丙烯酸酰胺的丙烯酸树脂，进一步地是由式II单体化合物与丙烯酸或甲基丙烯酸、丙烯酸酯或甲基丙烯酸酯、苯乙烯类、含羟基基团的甲基丙烯酸酯、N-取代的马来酰亚胺类等单体的共聚物，其中，R4为H、烷基或取代烷基；R5为H、C1～C6的烷基、芳基或乙烯基或丙烯基；其它共聚单体为以下单体一种或几种的组合：
Figure PCTCN2015094577-appb-000002
(1)具有脂肪羟基丙烯酸酯和甲基丙烯酸丙烯酸酯如：丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯或甲基丙烯酸2-羟乙酯。
(2)丙烯酸烷酯如：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸己酯、丙烯酸癸酯、丙烯酸苯叉酯、丙烯酸2－氯乙酯、丙烯酸缩水甘油酯。
(3)甲基丙烯酸烷酯如：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸己酯、甲基丙烯酸癸酯、甲基丙烯酸苯叉酯、甲基丙烯酸2－氯乙酯、甲基丙烯酸环己酯、丙烯酸聚乙二醇酯、甲基丙烯酸聚乙二醇酯、甲基丙烯酸月桂酯、甲基丙烯酸十八烷酯或甲基丙烯酸缩水甘油酯。
(4)丙烯酰胺和甲基丙烯酰胺如：丙烯酰胺、甲基丙烯酰胺、N-甲氧基丙烯酰胺、N-己基甲基丙烯酰胺、N-环己基丙烯酰胺、N-羟乙基丙烯酰胺、N-苯基丙烯酰胺、N-硝基苯基丙烯酰胺、N－乙烯酰胺、N-羧基苯基甲基丙烯酰胺或N-苯基N-乙基丙烯酰胺。
(5)乙烯醚如：乙基乙烯醚、2－氯乙基乙烯醚、羟乙基乙烯醚、丙基乙烯醚、丁基乙烯醚、癸基乙烯醚或苯基乙烯醚。
(6)乙烯酯如：醋酸乙烯酯、醋酸氯乙烯酯、丁酸乙烯酯或苯甲酸乙烯酯。
(7)苯乙烯如：苯乙烯、1－甲基苯乙烯、甲基苯乙烯或氯甲基苯乙烯。
(8)乙烯酮如：甲基乙烯酮、乙基乙烯酮、丙基乙烯醚或苯基乙烯醚。
(9)乙烯如：乙烯、丙烯、含脲侧链烯类、丁烯、异丁烯或异丙烯。
(10)N－乙烯吡咯烷酮、丙烯腈或甲基丙烯腈。
(11)不饱和酰亚胺如：N-马来酰亚胺、N－丙烯酸酰亚胺、N－乙基甲基丙烯酰胺或N－丙基甲基丙烯酰胺。
(12)不饱和羧酸如：丙烯酸、甲基丙烯酸马来酸酐或衣康酸。
本耐化学品功能树脂的分子量在1000～100000之间，所述苄磺酰胺基丙烯酸酰胺单体的结构单元所占共聚物的质量分数为5％～70％，所述N-芳基马来酰亚胺结构单元所占共聚物的质量分数为5％～70％；所述耐化学品功能树脂在底层感光组合物中的质量百分含量75％～85％。
2、成膜树脂
成膜树脂是线性酚醛树脂，:线性酚醛树脂树脂是苯酚、m-甲酚、o-甲酚、p-甲酚、摩尔数比为3:7～7:3的苯酚和m-甲酚、摩尔数比为3:1～1.5:1苯酚和叔丁酚、摩尔数比为9:1～5:5的m-甲酚和p-甲酚、m-,o-甲酚、2，4-二甲酚、3，5-二甲酚、N-苯基马来酰亚胺改性的m-/p-混合甲酚中的一种或几种 酚类与甲醛按不同比例缩聚而成的线性酚醛树脂；其重均分子量为2000～20000或2000～10000或2500～7500，Mw/Mn为1.5～20或1.5～10。当分子量大于20000时，酚醛树脂的线性度下降，支化度增加，从而在碱显影液中的溶解度下降，显影遇到困难；分子量太小，显影过程中抗碱性太弱，易于产生光解脱膜现象，版材的耐印力弱，也影响到版材的分辨率及网点的还原性。成膜树脂添加量占顶层感光组合物总重量的质量百分比为53.5％～65％。
3、光敏化合物，即感光剂PAC
本发明所述阳图PS版和CTcP版感光组分中的光敏化合物是重氮萘醌磺酸酯类化合物，其酯化母体可以是低分子多元酚类化合物，也可以是线性酚醛树脂等高分子化合物。作为本发明中所用的感光剂是采用1,2-萘醌-2叠氮-4-磺酰氯/1,2-萘醌-2叠氮-5-磺酰氯与苯酚、间-甲苯酚、对-甲苯酚、连苯三酚等羟基化合物同甲醛、丙酮等含羰基化合物的缩聚物采用公知的方法进行酯化反应得到的1,2-萘醌-2重氮-4-磺酸酯类化合物或1,2-萘醌-2重氮-5-磺酸酯类化合物一种或两种，两类磺酸酯可以单独使用，也可以组合使用以保证版材具有较高的感光度的同时，又兼具良好的阻溶性，两种光敏化合物的组合比例为0.2:1～1:0.2或0.5:1～1:0.5。所述磺酸酯类化合物的酯化母体是低分子多元酚类化合物、连苯三酚-丙酮缩聚物和/或线性酚醛树脂，所述酯化母体的重均分子量为50～20000；Mw/Mn为1.5～20,羟基酯化率是最初羟基的10％～80％，光敏物质在顶层感光层中的质量分数为30％～40％。光敏剂用量太大，阻溶能力太强，显影困难，感光度低，分辨力也下降；光敏剂用量太少，阻溶能力不足，抗碱性差，易于产生光解脱膜现象，版材的耐印力较低。
4、光致产酸剂
本发明中所用光致产酸剂为在近紫外区及紫外区(320～450nm)可顺利发 生光分解反应的化合物，最佳光谱感应范围为350～420nm。可选具有代表性的三氯甲基三嗪类化合物如:1-苯基-3,5双三氯甲基三嗪,l-甲氧苯基-3,5双三氯甲基三嗪,l-对甲氧苯乙烯基-3,5双三氯甲基三嗪,l-甲氧苯基-3,5双三氯甲基三嗪等。光致产酸剂的用量占感光组合物总重量为0.1～0.5重量％。
5、着色染料
本发明中所用背景着色染料为维多利亚纯蓝、碱性艳蓝、油溶蓝、结晶紫、乙基紫、甲基紫或亚甲基蓝中的一种或几种的混合物，由于考虑到对紫外线的吸收会降低版材感度，优选维多利亚纯蓝、碱性艳蓝、油溶蓝，着色染料在感光层中质量百分含量为1％～3％。
其他添加树脂还可以为聚氨酯、缩醛树脂、丙烯酸树脂等
显影促进剂是羧酸、羧酸酐、磺酸及磷酸类化合物的一种或几种的混合物，优选为柠檬酸、酒石酸、马来酸、苯甲酸、苯二甲酸、羟基苯甲酸、二羟基苯甲酸、马来酸酐、苯酐、四氢化苯酐三氮唑等中的任意一种或一种以上。
二、版材的制造方法
下面就该种平版印刷版的具体制作过程详述如下。
1、支持体的表面处理
本发明使用的支持体可以是尺寸稳定的铝或其合金(例如与硅、铜、锰、镁、铬、锌、铅、秘、镍的合金)。通常可以使用在铝手册第4版(1990、轻金属协会发行)中记载的以往公知的材料。铝版可以为采用通常的半连续铸造法(DC法)制造的铝版，此外也可以为采用连续铸造压延法制造的铝版。作为连续铸造压延的方法，可以使用双辊法、带式浇铸法、块料浇铸法等。合金中异种元素的含量为10重量％以下。铝版的厚度优选约为0.lmm～0.6mm左右。此外，也可以使用层压或蒸镀了铝、铝合金的塑料膜或纸。
当支持体为铝版时，通常根据目的对其表面实施各种处理。作为一般的处理方法，首先通过对铝版进行脱脂或电解研磨处理和去污物处理，对铝表面进行清洁。然后，实施机械表面粗糙化处理或/和电化学表面粗糙化处理，给予铝版表面微细的凹凸。此外，有时还增加化学蚀刻处理和去污物处理。然后，为了提高铝版表面的耐磨耗，实施阳极氧化处理，然后根据需要对铝表面实施亲水化处理或/和封孔处理。在各处理间，为了使前面处理的处理液不带入下一处理，优选进行采用压料辊进行的液体去除和采用喷射等进行的水洗。此外，可以将电化学表面粗糙化处理中使用的电解液的溢流废液用作去污物处理液，但此时可以省略去污物处理后的水洗处理。
第一步：脱脂一电解研磨处理
将铝版上存在的压延油、自然氧化皮膜、污物等除去，以均匀地进行电化学的表面粗糙化为目的，在酸性水溶液中进行铝版的电解研磨处理，或在酸或碱水溶液中进行铝版的化学蚀刻处理。
第二步：电解研磨处理
可以使用公知的用于电解研磨的水溶液。优选以硫酸或磷酸为主体的水溶液，特别优选以磷酸为主体的水溶液。电流可以使用直流、脉冲直流、或交流，但优选连续直流。电解处理装置可以使用扁型槽、星型槽等公知的电解处理使用的装置。
第三步：在酸或碱水溶液中的化学蚀刻处理
在酸或碱水溶液中进行铝版的化学蚀刻处理可以使用这些公知的手段。液温优选为25～90℃，优选进行1～120秒钟处理。酸性水溶液的浓度优选质量分数为0.5％～25％。
第四步：去污物处理
在蚀刻处理后，当使用碱的水溶液进行了化学蚀刻时，由于在铝的表面生成污物，因此一般用磷酸、硝酸、硫酸、铬酸或含有这些在内的2种以上的酸的混酸进行去污物处理。使用的酸性水溶液可以溶解0～5重量％铝，在液温从常温到70℃下实施，处理时间优选1～30秒。此外，作为该酸性水溶液，可以使用在电化学表面粗糙化处理等中使用的电解液的废液，必须注意不使铝版干燥，去污物液中的成分析出。去污物处理结束后，为了不将处理液带入下一工序，优选进行采用压料辊进行的液体去除和采用喷射进行的水洗，但当下一工序为同一水溶液时，也可以省略水洗。
第五步：机械表面粗糙化处理
为了得到良好的铝支持体，通常是对铝版的表面磨砂目，赋予微细的凹凸。在该磨砂目中一般已知球粒化、刷粒化、金属丝粒化、喷砂粒化等机械表面粗糙化处理，但作为大量且连续的处理，刷粒化处理优异。具体地说，在铝版表面喷射硅砂、氢氧化铝等的浆液，以50500rpm使刷毛径0.2～0.9mm的尼龙刷辊旋转，进行机械表面粗糙化处理。刷的压入力的旋转驱动马达的消费电力(除去驱动马达的机械损失的实质电力).优选0.2～15kw。
第六步：电化学表面粗糙化处理
使用直流的电化学表面粗糙化处理的以盐酸或硝酸为主体的水溶液，可以在使用通常的交流的电化学表面粗糙化处理中使用的水溶液，可以在1～100g/L的盐酸或硝酸水溶液中添加1g/L到饱和的硝酸铝、硝酸钠、硝酸按等具有盐酸离子的盐酸或硝酸化合物的1个以上使用。
第七步：利用酸-碱性液化学蚀刻处理
以将机械表面粗糙化处理、电化学表面粗糙化处理中形成的微细的凹凸的砂眼的整面、污物等除去为目的，进行化学蚀刻处理。液温优选为25～90℃， 优选进行1～120秒钟处理。酸性水溶液的浓度优选0.5～25重量％，更优选在酸性水溶液中溶解的铝为0.5～5重量％。碱水溶液的浓度优选5～30重量％，更优选在碱水溶液中溶解的铝为1～30重量％。
第八步：阳极氧化处理
为了提高铝版表面的保水性、耐磨耗性，实施阳极氧化处理。作为铝版的阳极氧化处理中使用的电解质，如果形成多孔氧化皮膜，可以使用任何的电解质。通常使用硫酸、磷酸、草酸、铬酸、或它们的混合液。这些电解质的浓度因电解质的种类而适当决定。阳极氧化的处理条件因所使用的电解质而变，因此不能一概而论。阳极氧化皮膜的量优选为1.0g/m2以上，更优选2.0～6.0g/m2的范围。
第九步：封孔处理
在实施了阳极氧化处理后，根据需要对铝表面实施亲水化处理。在本方法中，在硅酸钠水溶液中将支持体浸渍，或进行电解处理。(其他处理(水洗、封孔))在各处理结束后，为了不将处理液带入下一工序，进行采用压料辊液体去除和采用喷射进行的水洗。优选在阳极氧化处理后实施封孔处理。该封孔处理通过在含有热水和无机盐或有机盐的热水溶液中浸渍以及采用水蒸汽浴进行。
2、感光层的形成
感光层组合物以重量2％～20％的固体成分浓度溶解、分散，涂布到上述经过亲水砂目化版基上并进行干燥。在感光层涂布量通常优选干燥后的重量为0.5～2.0g/m2，随着涂布量减少，用于获得图像的曝光量减少，膜强度降低。随着涂布量增多，曝光量增大，膜的强度增强。
感光层组合物的溶解于可以选择一种、二种或三种以上溶剂。作为本专利使用的溶剂，包括丙酮、甲基乙基酮、环己烷、醋酸乙酷、二氯乙烯、四氢吠 喃、甲苯、乙二醇单甲醚、乙二醇单乙醚、乙二醇二甲醚、丙二醇单甲醚、丙二醇单乙醚、乙酞丙酮、环己酮、双丙酮醇、乙二醇单甲醚乙酸酷、乙二醇乙醚乙酸酷、乙二醇单异丙醚、乙二醇单丁醚乙酸酷,3一甲氧基丙醇、甲氧基甲氧基乙醇、二甘醇单甲醚、二甘醇单乙醚、二甘醇二甲醚、二甘醇二乙醚、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯，一甲氧基丙基乙酸酯、N,N一二甲基甲酰胺、二甲基亚砜,γ一丁内酯、乳酸甲酯、乳酸乙酯等。这些溶剂可以单独或混合使用。
为了提高涂布表观，可以在阳图型平版印刷版的感光层中可以添加表面活性剂。
感光层的涂布方法，可以使用涂布刮棒的方法、挤出型涂布机涂布方法、旋转式涂布，浸泡涂布，网纹辊涂布，空气剪式涂布，辊式涂布，刮板涂布，帘式涂布等的方法、滚珠涂布机的方法等，但并不限于这些。
3、曝光及显影加工
本发明阳图型平版印刷版版材用曝光光源为碳弧灯、高压水银灯、氨灯、金属卤化物灯、荧光灯、钨灯、卤素灯、氦福激光、氢离子激光、FD-YAG激光、氦氖激光、半导体激光(350nm～450nm)、对感光层进行图像曝光，采用这些以往公知的射线进行图像曝光后，通过用碱性溶液进行显影处理，即版子浸渍于显影液中，在0～60℃、优选15～40℃左右的温度下，用刷子擦拭或喷淋等方法曝光区域的涂层溶解于显影液中而被从铝版基上清除，非曝光区域保留，这样在铝版支持体表面上形成图像。
平版印刷版制造方法可以进一步包括修版和上保护胶等过程。
四、版材的检测方法：
1、耐化学品性检测方法
经过上述方法得到的版材，裁切成l0cm*2cm的测试条，用混合溶剂进行浸泡实验，混合溶剂组成二丙酮醇：纯水＝4:1，用用爱色丽528型密度仪量取测试条一端的密度，将量取密度的一端浸泡到试验溶剂中，10分钟后取出，用干净的软布擦干，再用爱色丽528型密度仪量取浸泡处密度值。计算密度损失的差值，差值越大，耐溶剂性越差。
2、UV-CTP感光度测试
版材使用科雷UV-CTP制版机(UV426E3X+)制版，光源为405nm半导体激光，外鼓式，转速900rpm。自激光能量30mw开始，递增5mw曝光，最大激光能量为70mw。后用(虎丘hu.q PT-125显影机)显影，显影液用“黑木”HUV-PN系列显影液，加水1:4稀释，25℃显影25秒。当平网实际输出为50士0.5％时，所用激光能量为合适曝光能量，此处用激光能量代表感光度，数值越大感光度越低，数值越小感光度越高。
3、分辨率测定
用科雷UV-CTP制版机(UV426E3X+)制版，设备分辨率2540dpi对版面进行曝光(制作1～4像素阴线和阳线)。后用(虎丘hu.q PT-125显影机)显影，显影液用“黑木”HUV-PN系列显影液，加水1:4稀释，25℃显影25秒。以阴线阳线同时还原表示版材的分辨率，像素数越小代表分辨率越高。
4、显影宽容度检测:
在科雷UV-CTP制版机(UV426E3X+)制版机上，按照上述得到的最佳曝光量的值的1.3倍的曝光量进行曝光，后以不同的显影时间在23℃下显影(这里选择10s,20s,30s,40s)，此条件下，能够使版材达到使用要求(空白处不留底，密度OD值<0.29；涂层实地不减膜，密度OD值>1.43；网点还原3％～99％)的显影时间的最高值和最低值之差即为该版材的显影宽容度。
5、耐印率模拟实验
经过曝光显影处理的版材，裁切成8cm×30cm大小的样版，固定于一个在一可密封容量大约1000ml容器中，加入表一配方化学品，要求版面接触化学品，不停转动20分钟，考察版面涂层密度损失情况，用爱色丽528型密度仪测密度值，版面密度越小，涂层损失越大，耐印力越差。
表1模拟耐印实验配方
Figure PCTCN2015094577-appb-000003
6、UV油墨耐印力模拟实验
经过曝光处理的版材，裁切成8cm×30cm大小的样版，固定于一个在一可密封容量大约1000ml容器中，加入表二配方化学品，要求版面接触化学品，不停转动20分钟，考察版面涂层密度损失情况，用爱色丽528型密度仪测密度值，版面密度越小，涂层损失越大，耐印力越差。
表2 UV油墨模拟耐印实验配方
Figure PCTCN2015094577-appb-000004
Figure PCTCN2015094577-appb-000005
本发明的有益效果是：提高阳图UV-CTP版材的耐溶剂性，同时提高版材的感度、分辨率、显影宽容度及耐印力并且适合UV油墨印刷。以下结合实施例对本发明进行说明，但本发明并不受这些实施例的限定。
具体实施方式
合成实施例1
将甲基丙烯酸31.0g(0.36mol),氯甲酸乙酯39.1g(0.36mol)，乙腈200ml加入到500毫升带有搅拌、温度计、和恒压滴液漏斗的三口烧瓶中，开动搅拌将混合物搅匀。用冰水浴冷却混合物，在1小时内滴加36.4g(0.36mol)三乙胺。滴加完毕后，撤去冰水浴，将滴液漏斗换成冷凝器。在室温继续搅拌30分钟。向反应混合物中加入1-(4-氨基苯基)-N-甲基-甲基磺酰胺60.08g(0.30mol),将混合物在70℃搅拌反应1小时。将反应混合物冷却后加到1升水中并搅拌30分钟。然后过滤，用500ml水打浆洗涤,干燥后得到30克白色粉末状的N-[4-((N-甲基-氨基磺酰)甲基)苯基]-2甲基-2-丙烯酰胺。
合成实施例2
丙烯酸树脂FSR1的合成
在500ml四口烧瓶中，装上搅拌，冷凝管、滴液漏斗，通入氮气，加入乙基溶纤剂105克，过氧化二苯甲酰0.6g，上述APDMAA15g，开动搅拌溶解，加入甲基丙烯酸11.5g、苯乙烯3.5g甲基丙烯酸-2-羟乙酯10g,N-苯基马来酰亚胺5g，搅拌10分钟，开始升温到80℃，反应1小时，开始滴加混合单体(APDMAA15g、甲基丙烯酸11.5g、苯乙烯3.5g甲基丙烯酸-2-羟乙酯10g,N-苯基马来酰亚胺5g，溶入105ml乙基溶纤剂中)，在1小时内滴完，继续反应4小时，反应结束后，降至室温，加入0.5g对苯二酚(溶于50ml乙基溶纤剂 中)，搅拌10分钟，然后将反应混合液慢慢加入4升水中，得到白色固体，过滤，清洗三次，置于真空干燥箱内干燥，得到含本发明丙烯酸树脂FSR1，重均分子量MW通过凝胶渗透色谱(Aglilient Technologies 1120Compact LC)测定(GPC)，测定条件以聚苯乙烯为标准，GPC柱：708*300MM，检测仪波长：220nm，进样浓度:1.0mg/ml,进样体积20ul流动相：DMF，柱温：35℃。合成的树脂样品经过凝胶渗透色谱系统测定可以得到重均分子量MW、数均分子量Mn、分子量分布等性能指标，共聚物重均分子量MW＝20000。
合成实施例3
丙烯酸树脂FSR2的合成
在500ml四口烧瓶中，，装上搅拌，冷凝管、滴液漏斗，通入氮气，加入乙基溶纤剂105克，过氧化二苯甲酰0.6g，上述APDMAA15g，开动搅拌溶解，加入甲基丙烯酸甲酯13.5g、甲基丙稀酸1.5g、丙烯腈10g,N-苯基马来酰亚胺5g，搅拌10分钟，开始升温到80℃，反应1小时，开始滴加混合单体(APDMAA15g、甲基丙烯酸甲酯13.5g、甲基丙稀酸1.5g、丙烯腈10g,N-苯基马来酰亚胺5g，溶入105ml乙基溶纤剂中)，在1小时内滴完，继续反应4小时，反应结束后，降至室温，加入0.5g对苯二酚(溶于50ml乙基溶纤剂中)，搅拌10分钟，然后将反应混合液慢慢加入4升水中，得到白色固体，过滤，清洗三次，置于真空干燥箱内干燥，得到含本发明丙烯酸树脂FSR1，重均分子量MW通过凝胶渗透色谱(Aglilient Technologies 1120Compact LC)测定(GPC)，测定条件以聚苯乙烯为标准，GPC柱：708*300MM，检测仪波长：220nm，进样浓度:1.0mg/ml,进样体积20ul流动相：四氢呋喃，柱温：35℃。合成的树脂样品经过凝胶渗透色谱系统测定可以得到重均分子量MW、数均分子量Mn、分子量分布等性能指标，重均分子量MW＝30000。
合成实施例4
丙烯酸树脂FSR3的合成
在1000ml四口烧瓶中，，装上上搅拌，冷凝管、滴液漏斗，通入氮气，加入乙基溶纤剂400ml，过氧化二苯甲酰0.8g，上述APDMAA 7g，开动搅拌溶解，加入丙烯腈8g、甲基丙烯酸乙酯10g,丙烯磺酰胺12g，搅拌10分钟，开始升温到80℃，反应1小时，开始滴加混合单体(APDMAA 7g、甲基丙烯酸乙酯5g溶入50ml乙基溶纤剂中)，在1小时内滴完，继续反应4小时，反应结束后，降至室温，加入0.5g对苯二酚(溶于50ml乙基溶纤剂中)，搅拌10分钟，然后将反应混合液慢慢加入4升水中，得到白色固体，过滤，清洗三次，置于真空干燥箱内干燥，得到含本发明丙烯酸树脂FSR3，重均分子量MW通过凝胶渗透色谱(Aglilient Technologies 1120Compact LC)测定(GPC)，测定条件以聚苯乙烯为标准，GPC柱：708*300MM，检测仪波长：220nm，进样浓度:1.0mg/ml,进样体积20ul流动相：四氢呋喃，柱温：35℃。合成的树脂样品经过凝胶渗透色谱系统测定可以得到重均分子量MW、数均分子量Mn、分子量分布等性能指标，这里关注的重均分子量MW＝37000。
合成实施例5
丙烯酸树脂FSR4的合成
在1000ml四口烧瓶中，，装上上搅拌，冷凝管、滴液漏斗，通入氮气，加入乙基溶纤剂400ml，过氧化二苯甲酰0.6g，上述APDMAA 3g，开动搅拌溶解，加入甲基丙烯酸3g、苯乙烯5g、丙烯腈3g、N-苯基马来酰亚胺9g、丙烯酰胺15g，搅拌10分钟，开始升温到80℃，反应1小时，开始滴加混合单体(APDMAA 5g、N-苯基马来酰亚胺9g溶入50ml乙基溶纤剂中)，在1小时内滴完，继续反应4小时，反应结束后，降至室温，加入0.5g对苯二酚(溶于 50ml乙基溶纤剂中)，搅拌10分钟，然后将反应混合液慢慢加入4升水中，得到白色固体，过滤，清洗三次，置于真空干燥箱内干燥，得到本发明丙烯酸树脂FSR4，重均分子量MW通过凝胶渗透色谱(Aglilient Technologies 1120Compact LC)测定(GPC)，测定条件以聚苯乙烯为标准，GPC柱：708*300MM，检测仪波长：220nm，进样浓度:1.0mg/ml,进样体积20ul流动相：四氢呋喃，柱温：35℃。合成的树脂样品经过凝胶渗透色谱系统测定可以得到重均分子量MW、数均分子量Mn、分子量分布等性能指标，这里关注的重均分子量MW＝52000。
实施例2-4：
1.测试用铝版基的制备
实施例和比较例所使用的版基按照以下工艺处理优选铝板，经过以下处理得到亲水表面。
(1)铝版进行去污处理，用有机溶剂、酸或碱水清理表面，溶解量在5-8g/m2；
(2)电解砂目：要求版材图文部分的亲油性好，空白部分亲水性要好，空白部分亲水性能好需要通过对铝版进行砂目化，使空白的砂眼部分储水而不亲油，砂目的形成用电解法，用铝版和石墨作为两个电极，电解液：6-20g/l的盐酸溶液中，50HZ交流电，电流20-100A/dm2，液温30-60，电解时间5-90秒，控制Ra＝0.5-0.6um；
(3)阳极氧化，为了提高铝版表面的机械强度、增强耐磨性和提高亲水性要对铝版表面进行阳极氧化处理，用15％-30％的硫酸溶液里，20-60温度下，5-250秒电解处理，铝离子浓度：0.5-5g/l，使用直流电，电流1-15A/dm2，控制氧化膜＝2-3g/m2；
(4)封孔，电解和阳极氧化后的铝版表面微孔很多，封孔的目的就是将 这些微孔堵住，使用硅酸钠水溶液浸泡实现亲水化和封孔的目的。
按下述配方制备PS版感光层涂布液：
2.底层涂布液配制
(1)底层感光层涂布液配制投料表：
Figure PCTCN2015094577-appb-000006
(2)将制得的涂布液用旋转涂布的方式涂布到上述经过亲水砂目化版基上并进行干燥好的400*510*0.27mm的版基上。在150℃烘箱中干燥3分钟。甩涂时控制合适的转速，以最终得到的样版涂层厚度为0.9g/m2。这样的到底层样版D1—D4.
3.上层涂布液配制
(1)顶层感光涂布液配制投料表：
Figure PCTCN2015094577-appb-000007
Figure PCTCN2015094577-appb-000008
(2)将制得的涂布液用旋转涂布的方式涂布到涂有底层的样版D1—D4上。在120℃烘箱中干燥3分钟。甩涂时控制合适的转速，以最终得到的样版涂层厚度为0.8g/m2。这样的到底层样版T1—T4。
比较例1
按下述配方制备PS版感光层涂布液：
Figure PCTCN2015094577-appb-000009
Figure PCTCN2015094577-appb-000010
比较例2
按下述配方制备UV-CTP版感光层涂布液：
Figure PCTCN2015094577-appb-000011
将制得两种比较用涂布液用旋转涂布的方式涂布到经过亲水砂目化版基上并进行干燥好的400*510*0.27mm的版基上。在120℃烘箱中干燥3分钟。甩涂时控制合适的转速，以最终得到的样版涂层厚度为1.8g/m2。这样的到底层样版C1—C2.
实验结果：
表3 PS版检测结果
Figure PCTCN2015094577-appb-000012
表4数字制版检测结果
  感光度mv 显影宽容度 分辨力
T1 45 20 1像素
T2 50 25 2像素
T3 55 20 1像素
T4 55 20 2像素
C1 60 15 3像素
C2 60 10 3像素
通过以上试验结果能够充分证明本发明的结论。

Claims (8)

  1. 一种阳图PS版和CTcP平版印刷版版材，其特征在于：包括一个亲水层，所述亲水层上涂有底层，所述底层上涂有顶层，所述底层和顶层对可见光和紫外光敏感；所述底层感光层由耐化学品功能树脂、光敏化合物、显影促进剂和背景着色染料制备而成；所述顶层感光层由成膜树脂、光敏化合物、显影促进剂、光致产酸剂、背景着色染料制备而成；所述耐化学品功能树脂为式I表示的共聚物；所述共聚物的分子量在1000～100000之间；所述苄磺酰胺基丙烯酰胺单体的结构单元所占共聚物的质量分数为5％～70％，所述N-芳基马来酰亚胺结构单元所占共聚物的质量分数为5％～70％；所述耐化学品功能树脂在底层感光组合物中的质量百分含量为75～85％；
    Figure PCTCN2015094577-appb-100001
    其中，R代表氢、C1～C4烷基或芳基的一种；R1、R2和R3代表H或CH3；v、w、x、y、z分别代表各单体组分在共聚物分子中所占质量分数，所述质量分数为5％～70％；所述v、w、x、y、z各组分质量分数之和为100％。
  2. 根据权利要求1所述的阳图PS版和CTcP平版印刷版版材版材，其特征在于：所述光敏化合物是1,2-萘醌-2重氮-4-磺酸酯类化合物或1,2- 萘醌-2重氮-5-磺酸酯类化合物中的一种或两种，所述磺酸酯类化合物的酯化母体是低分子多元酚类化合物、连苯三酚-丙酮缩聚物和/或线性酚醛树脂，所述酯化母体的重均分子量为50～20000；Mw/Mn为1.5～20,羟基酯化率是最初羟基的10％～80％；光敏物质在底层感光层中的质量分数为2％～20％，光敏化合物在顶层感光组合物的质量百分含量为30％～40％。
  3. 根据权利要求1或2所述的阳图PS版和CTcP平版印刷版版材版材，其特征在于:所述显影促进剂是羧酸、羧酸酐、磺酸及磷酸类化合物的一种或几种的混合物，加入量为底层感光组合物质量百分含量的3％-10％，为顶层感光组合物中质量百分含量1％-5％。
  4. 根据权利要求1或2所述的阳图PS版和CTcP平版印刷版版材版材，其特征在于:所述背景着色染料为维多利亚纯蓝、碱性艳蓝、油溶蓝、结晶紫、乙基紫、甲基紫或亚甲基蓝中的一种或几种的混合物，所述着色染料在底层感光组合物中的质量百分含量为1-3％；在顶层感光组合物中的质量百分含量为0.1％-1％。
  5. 根据权利要求1所述的阳图PS版和CTcP平版印刷版版材，其特征在于:所述成膜树脂为线性酚醛树脂，重均分子量为2000～20000,Mw/Mn为1.5～20，所述成膜树脂在顶层感光组合物中的质量百分含量为53.5％～65％。
  6. 根据权利要求5所述的阳图PS版和CTcP平版印刷版版材，其特征在于:所述线性酚醛树脂树脂是苯酚、m-甲酚、o-甲酚、p-甲酚、摩尔数比为3:7～7:3的苯酚和m-甲酚、摩尔数比为3:1～1.5:1苯酚和叔丁酚、摩尔数比为9:1～5:5的m-甲酚和p-甲酚、m-,o-甲酚、2，4-二甲酚、3， 5-二甲酚、N-苯基马来酰亚胺改性的m-/p-混合甲酚中的一种或几种酚类与甲醛按不同比例缩聚而成的线性酚醛树脂；其重均分子量为2000～20000或2000～10000或2500～7500；其添加量占全部顶层感光组合物的质量百分比为53.5％～65％。
  7. 根据权利要求1所述的阳图PS版和CTcP平版印刷版版材，其特征在于:所述光致产酸剂为在近紫外区及紫外区可发生光分解反应的化合物，光谱感应范围为350～420nm，所述光致产酸剂在顶层感光组合物中的质量百分含量为0.1％～0.5％。
  8. 根据权利要求1或2或5或6任一项所述的阳图PS版和CTcP平版印刷版版材，其特征在于:PS版和CTcP版前体需要经过曝光和显影加工过程制成阳图PS版和CTcP平版印刷版版材，包括修版或上胶过程。
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