WO2011134142A1 - 喷墨打印直接制版的版材及喷墨打印方法 - Google Patents

喷墨打印直接制版的版材及喷墨打印方法 Download PDF

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Publication number
WO2011134142A1
WO2011134142A1 PCT/CN2010/072239 CN2010072239W WO2011134142A1 WO 2011134142 A1 WO2011134142 A1 WO 2011134142A1 CN 2010072239 W CN2010072239 W CN 2010072239W WO 2011134142 A1 WO2011134142 A1 WO 2011134142A1
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WIPO (PCT)
Prior art keywords
ink
resin
plate
solvent
dye
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PCT/CN2010/072239
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English (en)
French (fr)
Inventor
周海华
宋延林
Original Assignee
中国科学院化学研究所
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Application filed by 中国科学院化学研究所 filed Critical 中国科学院化学研究所
Priority to US13/806,700 priority Critical patent/US20130160666A1/en
Priority to EP10850475.4A priority patent/EP2572891B1/en
Priority to PCT/CN2010/072239 priority patent/WO2011134142A1/zh
Publication of WO2011134142A1 publication Critical patent/WO2011134142A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1066—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by spraying with powders, by using a nozzle, e.g. an ink jet system, by fusing a previously coated powder, e.g. with a laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/003—Printing plates or foils; Materials therefor with ink abhesive means or abhesive forming means, such as abhesive siloxane or fluoro compounds, e.g. for dry lithographic printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0058—Digital printing on surfaces other than ordinary paper on metals and oxidised metal surfaces

Definitions

  • the invention belongs to the field of printing plates, and particularly relates to plates for direct printing by inkjet printing and inkjet printing methods. Background technique
  • Lithographic offset printing has a dominant position in the Chinese printing industry because of its excellent performance.
  • the printing plate base mainly uses aluminum plate base, and other metal plate bases such as copper plate base and zinc plate base can also be used.
  • the aluminum plate base is usually anodized and grained (see CN85100875A).
  • a large aluminum plate based anodizing plant has a monthly energy consumption of 2 million. KWh, the cost is about 160,000 US dollars / month, the waste acid liquid discharge is: for every 10,000 square meters of aluminum plate, the waste acid liquid discharge is about 2 tons; the waste alkali liquid discharge is: 10,000 square meters of aluminum per production The basis of the base, the discharge of waste alkali is about 3 tons.
  • a large amount of waste acid and waste lye discharges cause large environmental pollution. Summary of the invention
  • One of the objects of the present invention is to provide an inkjet printing plate-making plate which can obtain excellent printing durability and resolution without performing electrolytic graining and anodization, thereby overcoming the prior art metal plate.
  • the environment causes damage to the environment caused by waste acid liquid and waste alkali liquid generated during electrolytic sanding and anodizing.
  • Another object of the present invention is to provide an ink jet printing method using the plate of the present invention.
  • an inkjet printing directly plated plate comprising a metal sheet, an adhesive layer coated on a surface of the metal sheet, and coated on the paste An ink repellent layer on the adhesive layer.
  • the binder contained in the binder layer is selected from the group consisting of epoxy resins, polyurethanes, polyolefins, polyesters, styrene-butadiene rubbers, gelatin, polyvinyl butyral, polyamides, rosin resins, At least one selected from the group consisting of polyvinyl alcohol, alkyd resin, polyvinyl acetate, and the like; and the polyolefin is at least one selected from the group consisting of polypropylene, polyvinyl chloride, and polystyrene.
  • the ink repellent layer is a mixture of a silicone rubber and a curing agent or a fluorine-containing resin.
  • the plate of the present invention may further comprise a protective layer covering the ink repellent layer, preferably a polymer film having a thickness of between 1 and 20 ⁇ m.
  • the polymer in the polymer film may be polyethylene, polypropylene, polypentene, polydiene, poly At least one of propadiene, polyvinyl alcohol, polyglycolal butylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride resin, and the like.
  • the adhesive layer is obtained by coating a binder sol and drying, wherein the coated binder sol is composed of a solute and a solvent, and the concentration of the solute in the binder sol may be 0.05 to 15 wt. %, the coating amount of the binder sol may be 0.001 to 10 g/m 2 .
  • the binder layer is preferably coated on the entire surface of the metal sheet.
  • the solute in the binder is selected from the group consisting of epoxy resin, polyurethane, polyolefin, polyester, styrene-butadiene rubber, gelatin, polyvinyl butyral, polyamide, rosin resin, polyvinyl alcohol, At least one of the group consisting of an alkyd resin, polyvinyl acetate, and the like.
  • the polyolefin is at least one selected from the group consisting of polypropylene, polyvinyl chloride, and polystyrene.
  • the solvent in the binder may be at least one selected from the group consisting of water, ethanol, a dibasic acid ester, cyclohexane, heptane, tetrahydrofuran, and a common aromatic solvent.
  • the aromatic solvent is at least one selected from the group consisting of benzyl alcohol, phenylethyl alcohol, xylene, ethylbenzene, and toluene.
  • the ink repellent layer is obtained by coating a mixture of a silicone rubber and a curing agent or an organic solution coated with a fluorine resin, and drying the mixture, wherein a mixing ratio of the mixed silicone rubber and the curing agent is The type of silicone rubber used is determined. Generally, the mass ratio of the silicone rubber to the curing agent may be 5:1 to 15:1, and the coating amount of the silicone rubber and the curing agent may be 0.001 to 5 g/m 2 ; The content of the fluorine-containing resin in the mixed solution of the fluorine-containing resin and the organic solvent of the cloth may be 0.01 to 20% by weight, and the coating amount of the mixed solution of the fluorine-containing resin and the organic solvent may be 0.001 to 5 g/m 2 .
  • the ink repellent layer is preferably coated on the entire surface of the metal sheet.
  • the silicone rubber is preferably polydimethylsiloxane, and/or one or two methyl groups in the polydimethylsiloxane are vinyl, phenyl, alkyl having 2 carbon atoms or halogen. a product substituted by a phenyl group (the halogen is Cl, Br or 1).
  • the curing agent is preferably a derivative of a silane or an organic carboxylate of a metal; the derivative of the silane is preferably a silicone oil, a methyl silicone oil, an aminosilane, an aminopropylsilane, a methoxysilane, an ethoxy group. Silane or the like; the organic organic carboxylate of the metal is preferably dibutyltin laurate, and/or zinc chloroplatinate or the like.
  • the fluorine-containing resin may be at least one of a fluorine-containing acrylic resin, a fluorine-containing isocyanate resin, a fluorine-containing epoxy resin, and a fluorine-containing polyolefin resin.
  • the olefin in the fluorine-containing polyolefin resin is at least one selected from the group consisting of polypropylene, polyvinyl chloride, and polystyrene.
  • the organic solvent may be at least one selected from the group consisting of dimethyl sulfoxide, xylene, butyl acetate, ethylene glycol, propylene glycol, butanol, acetone, chloroform and the like.
  • the metal plate may be an aluminum plate base for ordinary printing production or an alloy plate base.
  • the alloy plate base may be an alloy plate base of silica and aluminum, and the alloy plate base has a silica content of 30 to 60% by weight. Adding 30 to 60% of silica to the total amount of silica and aluminum during aluminum smelting, and aluminum-zinc alloy sheet containing 1 to 3 wt% of zinc or aluminum-iron alloy sheet containing 0.1 to 1 wt% of iron. base. It is preferred to use an aluminum plate base or an aluminum alloy plate containing silica.
  • the metal plate may be subjected to electrolytic graining and anodization, and preferably not subjected to electrolytic graining and anodizing to avoid generation of waste acid liquid and waste alkali liquor to the environment. Come to harm.
  • the method for preparing the inkjet printing directly plated plate of the present invention may include: coating a surface of the metal plate with a binder sol composed of a solute and a solvent, drying and removing the solvent to obtain a binder layer; Coating the ink repellent, wherein the ink repellent is a mixture of a silicone rubber and a curing agent or a mixture of a fluorine resin and an organic solvent; drying, curing the silicone rubber to obtain a mixture of a silicone rubber and a curing agent The ink layer, or the organic solvent is removed by drying to obtain an ink repellent layer of a fluorine-containing resin, thereby obtaining the ink-jet printing directly plated plate.
  • the protective layer of the polymer film having a thickness of between 1 and 20 ⁇ m can be further coated on the obtained ink-jet-printed plate-making plate to obtain a plate of the ink-jet printing directly plated with a protective layer.
  • composition and coating amount of the binder sol have been described in detail above and will not be described herein.
  • composition and coating amount of the mixture of the silicone rubber and the curing agent and the organic solution of the fluorine-containing resin are described in detail above and will not be described herein.
  • the metal sheet material which is not subjected to electrolytic graining and anodizing treatment used in the present invention is coated with an ink repellent after being coated with a binder, thereby obtaining a plate material for inkjet printing directly, in the obtained ink jet.
  • the printing plate can be further covered with a protective layer of the polymer film, and the protective layer makes the plate less susceptible to scratching during transportation.
  • the effect of applying the binder on the surface of the metal sheet is to strengthen the adhesion between the metal plate base and the ink repellent liquid, and the resulting ink repellent layer has a non-stick printing during printing due to low surface tension during printing. The function of the ink.
  • an ink jet printing method comprising printing, by inkjet printing, graphic information on a plate of the present invention through a plate-making ink, and having graphic information
  • the plate is printed on the machine and printed.
  • the printing area printed with the plate-making ink is a graphic area, which is ink-receiving at the time of printing, and the area without the plate-making ink is a non-image area, which does not stick ink during printing, thereby realizing the graphic area and the non-graphic area.
  • the contrast of the area Excellent print durability and resolution can be obtained by using the plate of the present invention.
  • a method of printing graphic information on a plate through a plate-making ink, and a method of printing a plate having graphic information on the machine can be a conventional method in the art.
  • the plate-making ink may be various environmentally-friendly aqueous inks or solvent-based inks suitable for plate making.
  • the plate-making ink is a solvent-based ink, and the solvent-based plate-making ink comprises:
  • the printing durability and resolution can be further improved.
  • the preparation method of the solvent-based plate-making ink may include: mixing 1 to 35 wt% of the film-forming resin, 0.01 to 5 wt% of the curing agent, 0.01 to 10% of the nano- or micro-scale dye, and the balance solvent, room temperature The mixture was stirred, stirred until all of the solid solutes were dissolved, and the undissolved particles and impurities were removed by filtration, and the filtrate was the solvent-based plate-making ink of the present invention as described.
  • the film-forming resin in the plate-making ink is selected from the group consisting of a polyacrylic resin, a polymethacrylic resin, an esterified product of a polyacrylic resin, an esterified product of a polymethacrylic resin, a polyimide resin, a methyl silicone resin, and a poly Ester resin, epoxy resin, phenolic resin, polyurethane resin, benzoxazine resin, alkyd resin, rubber, polyamide, polyvinyl chloride, polystyrene, polycarbonate, polyphenylene ether, polysulfone, etc. At least one of the groups.
  • the esterified product of the polyacrylic resin includes an esterification reaction product of a polyacrylic resin and a monohydric alcohol having 5 carbon atoms.
  • the molar ratio of the polyacrylic resin to the monohydric alcohol may be 1:10 to 10:
  • the esterified product of the polymethacrylic resin comprises an esterification reaction product of a polymethacrylic resin and a monohydric alcohol having 5 carbon atoms, and a molar ratio of the polymethacrylic resin to the monohydric alcohol when the reactant is charged. Can be 1: 10 ⁇ 10: 1.
  • the curing agent in the plate-making ink may be selected from the group consisting of silicone oil, low molecular weight epoxy resin, dicyandiamide, melamine, ethanolamine, triethylamine, polyisocyanate, benzoyl peroxide, acetic anhydride, 2-ethylimidazole, At least one of the group consisting of 2,4-dimethylimidazole, pyromellitic dianhydride, and NN-dimethylaniline;
  • the low molecular weight epoxy resin may have an epoxy equivalent value of from 100 to 2000 g/eq.
  • the nano- or micro-sized dye in the plate-making ink may have a particle diameter of 10 to 3000 nm.
  • the dye in the plate-making ink may be selected from one of an acid dye, a reactive dye or a basic dye.
  • the acid dye may be one of Dye Acid Blue 9, Dye Acid Blue 9 SF, and Dye Acid Yellow 23 SF.
  • the reactive dye may be one of a black dye SP series or an active black.
  • the basic dye may be one of basic brilliant blue, hydrazine, and hydrazine-dimethylaniline in the blue dye.
  • the solvent in the plate making ink may be selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol Ether acetate, propylene glycol Ethyl acetate, propylene glycol butyl ether acetate, ethylene glycol butyl ether acetate, N, N-dimethylformamide, dioxane, sec-butyl acetate, grade A mineral oil, grade B mineral oil Kind.
  • the inkjet printing directly plated plate of the invention can obtain excellent printing durability and high resolution without electrolytic graining and anodizing of the metal plate, thereby avoiding electrolytic graining and anodizing process
  • the waste acid and waste lye in the middle cause large pollution to the environment.
  • the industrial aluminum plate which has not been subjected to electrolytic graining and anodizing is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, a surface of the aluminum plate is coated with a binder sol by spin coating.
  • the binder sol is a 0.05% by weight solution of an epoxy resin in benzyl alcohol, and the coating amount of the binder sol is 0.001 g/m 2 , and the benzyl alcohol is removed by drying to obtain an epoxy resin binder layer;
  • the ink repellent layer composed of polydimethylsiloxane and silicone oil is coated on the adhesive layer, and the mass ratio of polydimethylsiloxane to silicone oil is 5:1, and the coating amount of the ink repellent is 5 g/ m 2 , dried, and the polydimethylsiloxane is cured to obtain an ink repellent layer of a mixture of polydimethylsiloxane and silicone oil, thereby obtaining the ink-jet printing directly plated aluminum plate.
  • the resulting aluminum plate was further covered with a protective layer of a polyethylene film having a thickness of ⁇ .
  • Example 2 1 wt% of polyacrylic resin, 5 wt% of triethanolamine, 0.01 wt% of 3 ⁇ 4 basic brilliant blue (particle size of 10 nm), and the balance of ethylene glycol dimethyl ether constituting the solvent-based plate-making ink, and stirred at room temperature The mixed solution is stirred until the solid solute is completely dissolved, and the undissolved particles and impurities are removed by filtration, and the filtrate is the solvent-based plate-making ink.
  • Example 2 1 wt% of polyacrylic resin, 5 wt% of triethanolamine, 0.01 wt% of 3 ⁇ 4 basic brilliant blue (particle size of 10 nm), and the balance of ethylene glycol dimethyl ether constituting the solvent-based plate-making ink, and stirred at room temperature The mixed solution is stirred until the solid solute is completely dissolved, and the undissolved particles and impurities are removed by filtration, and the filtrate is the solvent-based plate-making ink.
  • Example 2
  • An industrial aluminum alloy plate (60 wt% containing silica) which is not subjected to electrolytic graining and anodizing treatment is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, washed with water, and spin-coated, in the aluminum alloy
  • the surface of the plate is coated with a binder sol.
  • the coated binder sol is a 15% by weight solution of epoxy resin in benzyl alcohol.
  • the coating amount of the binder sol is 10 g/m 2 , and the benzyl alcohol is removed by drying to obtain a ring.
  • An epoxy resin binder layer coating an epoxy resin layer composed of polymethylvinylsiloxane and methyl silicone oil on the epoxy resin binder layer, polymethylvinylsiloxane and methyl silicone oil
  • the mass ratio is 15:1
  • the coating amount of the ink repellent is 0.001 g/m 2
  • the polymethylvinylsiloxane is dried to obtain an ink repellent layer of a mixture of polymethylvinylsiloxane and silicone oil.
  • the ink-jet printing directly plated aluminum plate material is obtained. Further covering the obtained aluminum plate with a polypropylene film having a thickness of 20 ⁇ m Protective layer.
  • the industrial aluminum plate which has not been subjected to electrolytic graining and anodizing is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, a surface of the aluminum plate is coated with a binder sol by spin coating.
  • the binder sol is 0.05 wt% of a xylene solution of polyurethane, the binder sol is coated in an amount of 1 g/m 2 , and the xylene is dried to obtain a polyurethane binder layer; coated on the polyurethane binder layer An ink repellent consisting of a dimethyl sulfoxide solution of a fluorine-containing isocyanate resin having a concentration of 20% by weight, an ink repellent coating amount of 5 g/m 2 , and drying to remove dimethyl sulfoxide to obtain a fluorine-containing isocyanate resin. An ink repellent layer is obtained, thereby obtaining the ink-printed directly plated aluminum plate. The resulting aluminum plate was further covered with a protective layer of a polypentene film having a thickness of ⁇ .
  • An industrial aluminum alloy plate (containing 40% by weight of silica) which is not subjected to electrolytic graining and anodizing treatment is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, by spin coating, in the aluminum alloy
  • the surface of the plate is coated with a binder sol, the coated binder sol is a 15% by weight solution of polyurethane in xylene, the coating amount of the binder sol is 2 g/m 2 , and the xylene is dried to obtain a polyurethane binder.
  • an ink repellent solution consisting of a xylene solution of a fluorine-containing acrylic resin having a concentration of 0.01% by weight is applied onto the polyurethane adhesive layer, and the coating amount of the ink repellent is 0.001 g/m 2 , and the xylene is dried and removed.
  • An ink repellent layer of a fluorine-containing acrylic resin was obtained, whereby the ink-jet-printed aluminum plate material was obtained.
  • the resulting aluminum plate was further covered with a protective layer of a polyvinylidene film having a thickness of ⁇ .
  • An industrial aluminum alloy plate (containing 30% by weight of silica) which is not subjected to electrolytic graining and anodizing treatment is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, by spin coating, in the aluminum alloy
  • the surface of the plate is coated with a binder sol.
  • the coated binder sol is a 0.05% polystyrene solution in tetrahydrofuran, and the coating amount of the binder sol is 1.5 g/m 2 .
  • the tetrahydrofuran is removed by drying to obtain polyphenylene.
  • a vinyl binder layer an ink repellent composed of polymethylphenylsiloxane and dibutyltin laurate, polymethylphenylsiloxane and dibutyltin laurate coated on the polystyrene binder layer
  • the mass ratio is 6:1
  • the coating amount of the ink repellent is 2g/m 2
  • the polymethylphenylsiloxane is cured to obtain a mixture of polymethylphenylsiloxane and dibutyltin laurate.
  • An ink repellent layer is obtained, thereby obtaining the ink-printed directly plated aluminum plate.
  • the obtained aluminum plate was further covered with a protective layer of a polypropylene film having a thickness of 5 ⁇ m.
  • An industrial aluminum alloy plate (60 wt% containing silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating.
  • Applying a binder sol on the surface of the aluminum alloy plate the coated binder sol is a 15 wt% polystyrene solution of styrene, and the coating amount of the binder sol is 2.5 g/m 2 , and the benzene is removed by drying.
  • Ethanol to obtain a polystyrene binder layer coating an ink repellent composed of polymethylethylsiloxane and aminosilane on the polystyrene binder layer, polymethylethylsiloxane and amino group
  • the mass ratio of silane is 8:1
  • the coating amount of the ink repellent is lg/m 2
  • drying, the polymethylethylsiloxane is cured to obtain a mixture of polymethylethylsiloxane and aminosilane.
  • the ink layer thereby obtaining the ink-printed directly plated aluminum plate.
  • the resulting aluminum plate was further covered with a protective layer of a polyvinyl alcohol film having a thickness of 12 ⁇ m.
  • An industrial aluminum alloy plate (containing 40% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol to the surface of the aluminum alloy plate, the coated binder sol is an aqueous solution of 0.05% by weight of gelatin, and the coating amount of the binder sol is 4 g/m 2 , and the water is removed by drying to obtain gelatin.
  • an ink repellent solution consisting of a butyl acetate solution of a fluorine-containing epoxy resin having a concentration of 0.01 wt% is coated on the gelatin adhesive layer, and the coating amount of the ink repellent is 0.005 g/m 2 .
  • the butyl acetate was removed by drying to obtain an ink repellent layer of a fluorine-containing epoxy resin, whereby the ink-jet-printed aluminum plate material was obtained.
  • the resulting aluminum plate was further covered with a protective layer of a polyvinyl butyral film having a thickness of 6 ⁇ m.
  • An industrial aluminum alloy plate (containing 50% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol to the surface of the aluminum alloy plate, the coated binder sol is an aqueous solution of 15% by weight of gelatin, and the coating amount of the binder sol is 1.5 g/m 2 , and the water is removed by drying to obtain gelatin.
  • an ink repellent solution consisting of a solution of a fluorine-containing polyethylene resin having a concentration of 20% by weight of ethylene glycol (40 wt%) and a propylene glycol (40 wt%) on a gelatin adhesive layer, and coating of an ink repellent solution
  • the amount of cloth was 3 g/m 2 , and ethylene glycol and propylene glycol were removed by drying to obtain an ink repellent layer of a fluorine-containing polyethylene resin, whereby the ink-jet-printed aluminum plate material was obtained.
  • the resulting aluminum plate was further covered with a protective layer of a polystyrene film having a thickness of 3 ⁇ m.
  • the reaction product of a 5 wt% polymethacrylic resin constituting a solvent-based plate-making ink and methanol (the molar ratio of polymethacrylic acid: methanol is 1:2 when the reactant is charged), and the epoxy equivalent value of 0.03% by weight 100 g / equivalent of epoxy resin, lwt% of basic brilliant blue (particle diameter of 2000 nm), and the balance of propylene glycol ether vinegar
  • the acid ester is mixed; the mixture is stirred at room temperature, stirred until the solid solute is completely dissolved, and the undissolved particles and impurities are removed by filtration, and the filtrate is the solvent-based plate-making ink.
  • An industrial aluminum alloy plate (containing 30% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating.
  • Applying a binder sol on the surface of the aluminum alloy plate the coated binder sol is a 0.05 wt% ethanol solution of an alkyd resin, and the coating amount of the binder sol is 0.5 g/m 2 , and the ethanol is removed by drying.
  • an alkyd resin binder layer coating an ink repellent liquid composed of polymethylpropylsiloxane and aminopropylsilane on the alkyd resin binder layer, polymethylpropylsiloxane and The mass ratio of aminopropyl silane is 10: 1, the coating amount of the ink repellent is 0.01 g/m 2 , and the polymethyl propyl siloxane is cured to obtain polymethyl propyl siloxane and ammonia propylene.
  • the ink repellent layer of the mixture of silanes thereby obtaining the ink-jet printing directly plated aluminum plate.
  • the resulting aluminum plate was further covered with a protective layer of a polyethylene terephthalate film having a thickness of 16 ⁇ m.
  • Example 10 20% by weight of a polyester resin constituting a solvent-based plate-making ink, 0.02% by weight of benzoyl peroxide, 0.02% of a black dye SP (particle diameter of 3000 nm), and the balance of propylene glycol butyl ether acetate; stirring at room temperature The mixed solution is stirred until the solid solute is completely dissolved, and the undissolved particles and impurities are removed by filtration, and the filtrate is the solvent-based plate-making ink.
  • a polyester resin constituting a solvent-based plate-making ink
  • benzoyl peroxide 0.02%
  • a black dye SP particle diameter of 3000 nm
  • An industrial aluminum alloy plate (containing 30% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol to the surface of the aluminum alloy plate, the coated binder sol is a 15 wt% ethanol solution of an alkyd resin, and the coating amount of the binder sol is 0.02 g/m 2 , and the ethanol is dried and removed.
  • an alkyd resin binder layer coating an ink repellent liquid composed of polymethylcyclohexylsiloxane and dibutyltin laurate on the alkyd resin binder layer, polymethylcyclohexylsiloxane and laurel
  • the mass ratio of dibutyltin acid is 12:1
  • the coating amount of the ink repellent is 0.005 g/m 2
  • the polymethylcyclohexylsiloxane is cured to obtain polymethylcyclohexylsiloxane and lauric acid.
  • the obtained aluminum plate was further covered with a protective layer of a polyvinyl chloride film having a thickness of 9 ⁇ m.
  • the industrial aluminum plate which was not subjected to electrolytic graining and anodizing was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating.
  • Applying a binder sol on the surface of the aluminum plate the coated binder sol is a 0.05 wt% polyester dibasic acid ester solution, and the binder sol is coated in an amount of 0.005 g/m 2 , and dried to remove two a meta-ester to obtain a polyester binder layer; an ink repellent solution consisting of a butanol solution having a concentration of 0.01 wt% of a fluorine-containing acrylic resin is coated on the polyester binder layer, and the coating amount of the ink repellent is 4 g/m 2 , butanol was removed by drying to obtain an ink repellent layer of a fluorine-containing acrylic resin, whereby the ink-jet-printed aluminum plate material was obtained.
  • the obtained aluminum plate was further
  • An industrial aluminum alloy plate (containing 40% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol to the surface of the aluminum alloy plate, the coated binder sol is a 15 wt% polyester dibasic acid ester solution, and the binder sol is coated in an amount of 0.01 g/m 2 , dried and removed.
  • an ink repellent solution composed of an acetone solution having a concentration of 20% by weight of a fluorine-containing epoxy resin is coated on the polyester binder layer, and the coating amount of the ink repellent liquid is 0.2 g/m 2 , acetone was removed by drying to obtain an ink repellent layer of a fluorine-containing epoxy resin, whereby the ink-jet-printed aluminum plate material was obtained.
  • the resulting aluminum plate was further covered with a protective layer of a polyethylene terephthalate film having a thickness of 2 ⁇ m.
  • Example 13 An industrial aluminum alloy plate (containing 45 wt% of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol to the surface of the aluminum alloy plate, the coated binder sol is an aqueous solution of 0.05 W t% of polyvinyl alcohol, and the coating amount of the binder sol is 0.06 g/m 2 , and the water is removed by drying.
  • obtaining a polyvinyl alcohol binder layer coating an ink repellent liquid composed of polymethyl isobutylsiloxane and methoxysilane on the polyvinyl alcohol binder layer, polymethyl isobutyl silicon oxide
  • the mass ratio of the alkane to the methoxysilane is 9 : 1
  • the coating amount of the ink repellent is 2.5 g / m 2
  • the polymethyl isobutyl siloxane is cured to obtain a polymethyl isobutyl siloxane.
  • the resulting aluminum plate was further covered with a protective layer of a polypentene film having a thickness of 13 ⁇ m.
  • the reaction product of a 35 wt% polyacrylic resin and a pentanol constituting a solvent-based plate-making ink (the molar ratio of the polyacrylic resin:pentanol is 1:2 when the reactant is charged), 0.02 wt% of diethanolamine, 1% Dye acid yellow 23 SF (particle diameter is 2000 nm), and the balance of sec-butyl acetate mixed; stir the mixture at room temperature, stir until the solid solute is completely dissolved, filter to remove undissolved particles and impurities, the filtrate is the solvent Type plate ink.
  • An industrial aluminum alloy plate (containing 35 wt% of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating.
  • obtaining a polyvinyl alcohol binder layer coating an ink repellent liquid composed of polyethylvinylsiloxane and ethoxysilane on the polyvinyl alcohol binder layer, polyethylvinylsiloxane and The mass ratio of ethoxysilane was 7:1, the coating amount of the ink repellent was 1.5 g/m 2 , and the polyethylvinylsiloxane was cured to obtain polyethylvinylsiloxane and ethoxylate.
  • the ink repellent layer of the mixture of silanes thereby obtaining the ink-jet printing directly plated aluminum plate.
  • the resulting aluminum plate was further covered with a protective layer of a polypropene film having a thickness of ⁇ .
  • the ink composition of the solvent type plate 35wt% polyvinyl chloride, 0.02wt% of diethanolamine, l W t% of the dye Acid Yellow 23 SF (particle diameter of 2000nm) A mixing stage mineral oil, and the balance; stirred at room temperature The mixed solution is stirred until the solid solute is completely dissolved, and the undissolved particles and impurities are removed by filtration, and the filtrate is the solvent-based plate-making ink.
  • An industrial aluminum alloy plate (60 wt% containing silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating.
  • Ethylbenzene obtaining a polyvinyl acetate binder layer; coating a polyvinyl acetate adhesive layer with an ink repellent consisting of a chloroform solution having a concentration of 2 (1% of fluorine-containing isocyanate, an ink repellent liquid
  • the coating amount was 0.5 g/m 2
  • chloroform was removed by drying to obtain an ink repellent layer of a fluorine-containing isocyanate, thereby obtaining the ink-jet-printed aluminum plate material.
  • the obtained aluminum plate was further covered with a thickness of ⁇ .
  • Protective layer of polystyrene film was further covered with a thickness of ⁇ .
  • An industrial aluminum alloy plate (containing 30% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol to the surface of the aluminum alloy plate, the coated binder sol is a 15% solution of polyvinyl acetate in ethylbenzene, and the coating amount of the binder sol is 9 g/m 2 , and drying is performed to remove B.
  • Benzene obtaining a polyvinyl acetate binder layer; coating an ink repellent solution composed of a fluoroethylene solution having a concentration of 0.01 wt% of fluorine-containing polyethylene on the polyvinyl acetate binder layer, and repelling ink
  • the coating amount of the liquid was 3 g/m 2 , and dimethyl sulfoxide was removed by drying to obtain an ink repellent layer of a fluorine-containing polyethylene, whereby the ink-jet-printed aluminum plate material was obtained.
  • the obtained aluminum plate was further covered with a protective layer of a polyvinyl butyral film having a thickness of 5 ⁇ m.
  • Industrial aluminum alloy sheet (containing 32% by weight of silica) without electrolytic sanding and anodizing
  • the oil was removed by an aqueous solution of 5 wt% diluted sodium hydroxide, and after washing with water, a binder sol was applied on the surface of the aluminum alloy plate by spin coating, and the coated binder sol was 0.9 wt% of polyvinyl alcohol.
  • a benzyl alcohol solution of butyraldehyde a coating amount of the binder sol is 0.015 g/m 2 , and benzyl alcohol is removed by drying to obtain a polyvinyl butyral adhesive layer; in a polyvinyl butyral adhesive layer Applying an ink repellent consisting of polydimethylsiloxane and silicone oil, the mass ratio of polydimethylsiloxane to silicone oil is 7:1, and the coating amount of the ink repellent is 5g/m 2 , drying The polydimethylsiloxane is cured to obtain an ink repellent layer of a mixture of polydimethylsiloxane and silicone oil, thereby obtaining the ink-jet printing directly plated aluminum plate. The resulting aluminum plate was further covered with a protective layer of a polyethylene film having a thickness of ⁇ .
  • Example 18 5%% of the polyurethane resin constituting the solvent-based plate-making ink, 5% by weight of triethanolamine, 0.01% by weight of basic brilliant blue (particle size of 10 nm), and the balance of ethylene glycol dimethyl ether, and stirred at room temperature The mixed solution is stirred until the solid solute is completely dissolved, and the undissolved particles and impurities are removed by filtration, and the filtrate is the solvent-based plate-making ink.
  • An industrial aluminum alloy plate (containing 50% by weight of silica) which is not subjected to electrolytic graining and anodizing treatment is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, by spin coating, in the aluminum alloy
  • the surface of the plate is coated with a binder sol, the coated binder sol is a 10% by weight solution of a polyamide in xylene, the coating amount of the binder sol is 6 g/m 2 , and the xylene is dried to obtain a polyamide adhesive.
  • a coating layer coating an ink repellent liquid composed of polymethylvinylsiloxane and methyl silicone oil on the polyamide adhesive layer, and the mass ratio of polymethylvinylsiloxane to methyl silicone oil is 8 : 1, the coating amount of the ink repellent is 0.001 g / m 2 , dried, and the polymethylvinylsiloxane is cured to obtain an ink repellent layer of a mixture of polymethylvinylsiloxane and silicone oil, thereby obtaining The inkjet printed directly plated aluminum plate.
  • the resulting aluminum plate was further covered with a protective layer of a polypropylene film having a thickness of 20 ⁇ m.
  • An industrial aluminum alloy plate (containing 45 wt% of silica) which is not subjected to electrolytic graining and anodizing treatment is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, by spin coating, in the aluminum alloy
  • the surface of the plate is coated with a binder sol.
  • the coated binder sol is a 1.5 wt% solution of rosin resin in cyclohexane.
  • the coating amount of the binder sol is 1.2 g/m 2 , and the cyclohexane is removed by drying.
  • a rosin resin binder layer in a rosin resin binder layer
  • An ink repellent solution consisting of a dimethyl sulfoxide solution having a concentration of 20% by weight of a fluorine-containing isocyanate resin was applied thereto, and the coating amount of the ink repellent liquid was 5 g/m 2 , and dimethyl sulfoxide was removed by drying to obtain a fluorine-containing solvent.
  • An ink repellent layer of an isocyanate resin thereby obtaining an ink-jet-printed aluminum plate material.
  • the resulting aluminum plate was further covered with a protective layer of a polypentene film having a thickness of ⁇ .
  • Example 20 15 wt% of benzoxazine resin, 2 W t% of polyisocyanate, 10 wt% of dye acid blue 9 (particle size of 2000 nm), and the balance of ethylene glycol mono-n-butyl ether The mixture was stirred at room temperature, stirred until the solid solute was completely dissolved, and the undissolved particles and impurities were removed by filtration, and the filtrate was the solvent-based plate-making ink.
  • Example 20 15 wt% of benzoxazine resin, 2 W t% of polyisocyanate, 10 wt% of dye acid blue 9 (particle size of 2000 nm), and the balance of ethylene glycol mono-n-butyl ether The mixture was stirred at room temperature, stirred until the solid solute was completely dissolved, and the undissolved particles and impurities were removed by filtration, and the filtrate was the solvent-based plate-making ink.
  • Example 20
  • An industrial aluminum alloy plate (containing 40% by weight of silica) which was not subjected to electrolytic graining and anodizing treatment was degreased with an aqueous solution of 5 wt% of dilute sodium hydroxide, washed with water, and then applied by spin coating. Applying a binder sol on the surface of the aluminum alloy plate, the coated binder sol is a 3% by weight heptane solution of styrene-butadiene rubber, and the coating amount of the binder sol is 0.04 g/m.
  • the ink repellent the mass ratio of polymethylcyclohexylsiloxane to dibutyltin laurate is 10:1, the coating amount of the ink repellent is 0.01 g/m 2 , and drying, making polymethylcyclohexylsiloxane
  • the alkane is solidified to obtain an ink repellent layer of a mixture of polymethylcyclohexylsiloxane and dibutyltin laurate, whereby the ink-jet-printed aluminum plate material is obtained.
  • the obtained aluminum plate was further covered with a protective layer of a polyvinyl chloride film having a thickness of 9 ⁇ m.
  • the solvent-based plate-making inks prepared in the above Examples 1 to 20 were sprayed on the aluminum plate of the inkjet printing directly plated obtained in the respective examples by using an inkjet printer (the protective layer was removed) to form an image;
  • the aluminum plate of the plate-making ink is baked at 90-300 ° C, and the plate-making ink is cross-linked and cured under the action of a curing agent in the plate-making ink, and the aluminum plate after the above treatment is printed on the machine and passed the test.
  • the printing plate has excellent printing suitability and printing durability up to about 100,000 sheets.
  • the resolution of the printing medium line can reach ⁇ , and 5 ⁇ 95% of the dots can be completely clear.
  • Blackjet ink (SPECTRA, UK) was sprayed on the ink-jet printing directly plated aluminum plate obtained in Examples 1-20 using an inkjet printer (removing the protective layer) to form an image; then the aluminum coated with the plate-making ink was sprayed
  • the plate is baked at 90 ⁇ 300 °C, so that the plate-making ink is cross-linked and cured under the action of the curing agent in the plate-making ink, and the aluminum plate after the above treatment is printed on the machine, and the printing is printed by the printing.
  • the performance is excellent and the printing durability can reach 10,000 or so.
  • the resolution of the printing medium line can reach 20 ⁇ , and the 10 ⁇ 90% dot can be completely clear.
  • Seiko ink SOLVENT INK, Japan was sprayed on the ink-jet printing directly plated aluminum plate obtained in Examples 1-20 using an inkjet printer (removing the protective layer) to form an image; then the plate-making ink was sprayed
  • the aluminum plate is baked at 90 ⁇ 300 °C, so that the plate-making ink is cross-linked and cured under the action of the curing agent in the plate-making ink, and the aluminum plate after the above treatment is printed on the machine, and the printing of the plate is detected.
  • the applicability is excellent and the printing durability can reach 50,000 or so.
  • the resolution of the printed graphic middle line can reach 15 ⁇ , and the 5 ⁇ 90% dot can be completely clear. Comparative example 1
  • Industrial aluminum alloy plate (containing 40% by weight of silica) after electrolytic graining and anodizing treatment (electrolysis twice in 1% hydrochloric acid aqueous solution for 30 seconds; anodizing in 15% sulfuric acid aqueous solution 30 Seconds) Degrease with an aqueous solution of 5 wt% dilute sodium hydroxide. After washing with water, an ink (SPT510, China) was sprayed on the inkjet printer to form an image; then the aluminum plate coated with the plate-making ink was passed through 90 to 300°.
  • the plate-making ink is cross-linked and cured under the action of the curing agent in the plate-making ink, and the aluminum plate after the above treatment is printed on the machine, and the printing property of the printing plate is excellent and the printing durability is good.
  • the resolution of the center line of the printing plate can reach 30 ⁇ , and 15 ⁇ 85% of the dots can be completely clear. Comparative example 2
  • An industrial aluminum alloy plate (containing 40% by weight of silica) which is not subjected to electrolytic graining and anodizing treatment is degreased with an aqueous solution of 5 wt% dilute sodium hydroxide, and after washing with water, an ink is used by an inkjet printer (P522-6) , China) forming an image on the spray; then baking the aluminum plate coated with the plate-making ink through 90 ⁇ 300 ° C, so that the plate-making ink is cross-linked and cured under the action of the curing agent in the plate-making ink, After processing, the aluminum plate is printed on the machine. Through inspection, the printing plate has excellent printability and the printing durability can reach about 200 sheets, and the resolution of the printing plate center line is only 900 ⁇ m.

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Description

喷墨打印直接制版的版材及喷墨打印方法
技术领域
本发明属于印刷版材领域， 具体涉及喷墨打印直接制版的版材及喷墨打印方法。 背景技术
平版胶印印刷因为具有优异的性能而在中国印刷行业中占有主导地位， 目前印 刷版基主要使用铝板基， 也可使用铜板基、 锌板基等其它金属板基。 为了使铝板基 的耐印力及分辨率提高， 通常要对铝板基进行阳极氧化及砂目化处理 （见 CN85100875A) o 经调查， 一个大型铝板基阳极氧化处理厂每月电能消耗量为 200万 KWh, 成本约为 16万美元 /月， 废酸液排出量为： 每生产 1万平米铝版基， 废酸液 排出量约为 2吨； 废碱液排出量为： 每生产 1万平米铝版基， 废碱液排出量约为 3 吨。 大量的废酸液、 废碱液的排放造成了环境的较大污染。 发明内容
本发明的目的之一在于提供一种可以不进行电解砂目化和阳极氧化也能够得到 优良的耐印力和分辨率的喷墨打印直接制版的版材， 以克服现有技术中对金属版基 进行电解砂目化和阳极氧化时产生的废酸液、 废碱液给环境带来的危害。
本发明的另一目的在于提供一种使用本发明的版材的喷墨打印方法。
根据本发明的第一目的， 提供了一种喷墨打印直接制版的版材， 该版材包括金 属板材、 涂布在所述金属板材的表面的粘结剂层、 以及涂布在所述粘接剂层上的斥 墨层。
所述粘结剂层中所含的粘结剂选自环氧树脂、 聚氨酯、 聚烯烃、 聚酯、 苯乙烯- 丁二烯橡胶、 明胶、 聚乙烯醇縮丁醛、 聚酰胺、 松香树脂、 聚乙烯醇、 醇酸树脂、 聚醋酸乙烯酯等所组成的组中的至少一种； 所述的聚烯烃选自聚丙烯、 聚氯乙烯、 聚苯乙烯所组成的组中的至少一种。
所述的斥墨层是硅橡胶与固化剂的混合物或是含氟树脂。
本发明的版材还可以包括保护层， 该保护层覆盖在所述的斥墨层上， 优选为厚 度在 1〜20μηι之间的聚合物薄膜。
所述的聚合物薄膜中的聚合物可以为聚乙烯、 聚丙烯、 聚戊烯、 聚乙二烯、 聚 丙二烯、 聚乙烯醇、 聚乙醇縮丁醛、 聚苯乙烯、 聚对苯二甲酸乙二醇酯、 聚氯乙烯、 聚偏二氯乙烯树脂等中的至少一种。
所述的粘结剂层是涂布粘结剂溶胶并干燥后得到的， 其中， 涂布的粘结剂溶胶 是由溶质与溶剂组成，粘结剂溶胶中的溶质的浓度可以为 0.05〜15wt%，粘结剂溶胶 的涂布量可以为 0.001〜10g/m2。 粘结剂层优选涂布在金属板材的整个表面上。
所述的粘结剂中的溶质选自环氧树脂、 聚氨酯、 聚烯烃、 聚酯、 苯乙烯-丁二烯 橡胶、 明胶、 聚乙烯醇縮丁醛、 聚酰胺、 松香树脂、 聚乙烯醇、 醇酸树脂、 聚醋酸 乙烯酯等所组成的组中的至少一种。 所述的聚烯烃选自聚丙烯、 聚氯乙烯、 聚苯乙 烯所组成的组中的至少一种。
所述的粘结剂中的溶剂可以选自水、 乙醇、 二元酸酯、 环己烷、 庚烷、 四氢呋 喃、 常用芳香族溶剂所组成的组中的至少一种。 所述的芳香族溶剂选自苯甲醇、 苯 乙醇、 二甲苯、 乙苯、 甲苯所组成的组中的至少一种。
所述的斥墨层是涂布硅橡胶与固化剂的混合液或涂布含氟树脂的有机溶液并干 燥后得到的， 其中， 涂布的硅橡胶与固化剂的混合液的混合比例由所使用的硅橡胶 的种类决定， 一般硅橡胶与固化剂混合的质量比可以为 5: 1〜15： 1， 硅橡胶与固化 剂的混合液的涂布量可以为 0.001〜5g/m2; 涂布的含氟树脂与有机溶剂的混合液中 的含氟树脂的含量可以为 0.01〜20wt%，含氟树脂与有机溶剂的混合液的涂布量可以 为 0.001〜5g/m2。 斥墨层优选涂布在金属板材的整个表面上。
所述的硅橡胶优选为聚二甲基硅氧烷， 和 /或聚二甲基硅氧烷中的一个或两个甲 基被乙烯基、苯基、 2 碳原子数 6的烷基或卤代苯基取代的产物（所述卤素为 Cl、 Br或 1)。 所述的固化剂优选是硅烷的衍生物或金属的有机羧酸盐； 所述的硅烷的衍 生物优选是硅油、 甲基硅油、 氨基硅烷、 氨丙基硅烷、 甲氧基硅烷、 乙氧基硅烷等； 所述的金属的有机羧酸盐优选是月桂酸二丁基锡、 和 /或氯铂酸锌等。
所述的含氟树脂可以是含氟丙烯酸树脂、 含氟异氰酸酯树脂、 含氟环氧树脂、 含氟聚烯烃树脂等中的至少一种。 所述的含氟聚烯烃树脂中的烯烃选自聚丙烯、 聚 氯乙烯、 聚苯乙烯等中的至少一种。
所述的有机溶剂可以为二甲基亚砜、 二甲苯、 醋酸丁酯、 乙二醇、 丙二醇、 丁 醇、 丙酮、 氯仿等所组成的组中的至少一种。
所述的金属板材可以是普通印刷生产用的铝板基， 或是合金板基。 所述的合金 板基可以是二氧化硅与铝的合金板基，该合金板基的二氧化硅含量为 30〜60wt% (冶 炼铝时添加占二氧化硅和铝总量的 30〜60^%的二氧化硅），还可以使用含 l〜3wt% 锌的铝锌合金板基或含 0.1〜lwt%铁的铝铁合金板基。优选使用铝板基或含二氧化硅 的铝合金板。 根据本发明提供的版材， 所述的金属板材可以不进行电解砂目化和阳 极氧化， 并且优选不进行电解砂目化和阳极氧化， 以避免产生废酸液、 废碱液而给 环境带来危害。
本发明的喷墨打印直接制版的版材的制备方法可以包括： 在金属板材的表面涂 布由溶质与溶剂组成的粘结剂溶胶， 干燥除去溶剂， 得到粘结剂层； 在粘结剂层上 涂布斥墨液， 其中， 斥墨液是硅橡胶与固化剂的混合液或是含氟树脂与有机溶剂的 混合液； 干燥， 使硅橡胶固化得到是硅橡胶与固化剂的混合物的斥墨层， 或干燥除 去有机溶剂得到是含氟树脂的斥墨层， 由此得到所述的喷墨打印直接制版的版材。
在得到的喷墨打印直接制版的版材上可以进一步覆盖厚度在 1〜20μηι之间的聚 合物薄膜的保护层， 得到带有保护层的喷墨打印直接制版的版材。
所述粘结剂溶胶的组成和涂布量在上文已作详细描述， 此处不再赘述。
所述硅橡胶与固化剂的混合液以及含氟树脂的有机溶液的组成和涂布量在上文 已作详细描述， 此处不再赘述。
本发明使用的不经过电解砂目化和阳极氧化处理的金属板材， 在经过表面涂布 粘结剂后再涂布斥墨液， 从而得到喷墨打印直接制版的版材， 在所得的喷墨打印直 接制版的版材上可进一步覆盖聚合物薄膜的保护层， 保护层使版材在运输过程中不 易划伤。 在所述的金属板材表面涂布粘结剂的作用是加强金属版基与斥墨液之间的 粘结力， 所得斥墨层在印刷时由于低的表面张力而具有在印刷时不粘印刷油墨的功 能。
根据本发明的另一目的， 提供了一种喷墨打印方法， 该方法包括以喷墨打印的 方式， 将图文信息通过制版墨水打印在本发明的版材上， 将带有图文信息的版材上 机印刷， 得到印刷品。 打印有制版墨水的打印区域为图文区， 该区域在印刷时亲油 墨， 而没有制版墨水的区域为非图文区， 该区域在印刷时不粘油墨， 从而实现图文 区与非图文区的反差。 使用本发明的版材可以得到优良的耐印力和分辨率。
将图文信息通过制版墨水打印在版材上的方法、 以及将带有图文信息的版材上 机印刷的方法可以为本领域常规的方法。
如果所述版材包括所述保护层， 则在打印之前， 将保护层膜揭开， 去除掉。 所述制版墨水可以为各种适用于制版的环保型水性墨水或溶剂型墨水。 优选情况下， 所述制版墨水为溶剂型墨水， 该溶剂型制版墨水含有：
成膜树脂 l〜35wt%
固化剂 0.01〜5wt%
纳米级或微米级染料 0.01〜10wt%
溶剂 余量
按照该优选实施方式， 可以进一步提高耐印力和分辨率。
所述溶剂型制版墨水的制备方法可以包括： 将 l〜35wt%的成膜树脂、 0.01〜 5wt%的固化剂、 0.01〜10^%的纳米级或微米级染料及余量的溶剂混合， 室温搅拌 混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的本 发明的溶剂型制版墨水。
所述的制版墨水中的成膜树脂选自聚丙烯酸树脂、 聚甲基丙烯酸树脂、 聚丙烯 酸树脂的酯化物、 聚甲基丙烯酸树脂的酯化物、 聚酰亚胺树脂、 甲基硅树脂、 聚酯 树脂、 环氧树脂、 酚醛树脂、 聚氨酯树脂、 苯并噁嗪树脂、 醇酸树脂、 橡胶、 聚酰 胺、 聚氯乙烯、 聚苯乙烯、 聚碳酸酯、 聚苯醚、 聚砜等所组成的组中的至少一种。
所述的聚丙烯酸树脂的酯化物包括聚丙烯酸树脂与 1 碳原子数 5的一元醇的 酯化反应产物， 反应物投料时， 聚丙烯酸树脂与一元醇的摩尔比可以为 1 : 10〜10 ： 1 ; 所述的聚甲基丙烯酸树脂的酯化物包括聚甲基丙烯酸树脂与 1 碳原子数 5 的一元醇的酯化反应产物， 反应物投料时， 聚甲基丙烯酸树脂与一元醇的摩尔比可 以为 1： 10〜10： 1。
所述的制版墨水中的固化剂可以选自硅油、 低分子量环氧树脂、 双氰胺、 三聚 氰胺、 乙醇胺、 三乙胺、 多异氰酸酯、 过氧化苯甲酰、 乙酸酐、 2-乙基咪唑、 2， 4- 二甲基咪唑、 偏苯四酸二酐、 N-N-二甲基苯胺所组成的组中的至少一种；
所述的低分子量环氧树脂的环氧当量值可以为 100〜2000克 /当量。
所述的制版墨水中的纳米级或微米级染料的颗粒粒径可以为 10〜3000nm。
所述的制版墨水中的染料可以选自酸性染料、 活性染料或碱性染料中的一种。 所述的酸性染料可以是染料酸性蓝 9、染料酸性蓝 9 SF、染料酸性黄 23 SF中的 一种。所述的活性染料可以是黑色染料 SP系列或活性黑中的一种。所述的碱性染料 可以是蓝色染料中的碱性艳兰、 Ν,Ν—二甲基苯胺中的一种。
所述的制版墨水中的溶剂可以选自乙二醇单甲醚、 乙二醇单乙醚、 乙二醇单正 丁醚、 乙二醇二甲醚、 丙二醇单甲醚、 丙二醇单乙醚、 丙二醇甲醚醋酸酯、 丙二醇 乙醚醋酸酯、 丙二醇丁醚醋酸酯、 乙二醇丁醚醋酸酯、 N， N-二甲基甲酰胺、 二氧六 环、 乙酸仲丁酯、 A级矿精油、 B级矿精油中的一种。
本发明的喷墨打印直接制版的版材可以不对金属板材进行电解砂目化和阳极氧 化处理就能够获得优良的耐印力和高的分辨率， 从而避免了电解砂目化和阳极氧化 处理过程中废酸液、 废碱液对环境造成的较大污染。 具体实施方式
实施例 1
将不经过电解砂目化和阳极氧化处理的工业用铝板用 5wt%稀氢氧化钠的水溶 液除油， 水洗后， 以旋涂的方法， 在该铝板表面涂布粘结剂溶胶， 涂布的粘结剂溶 胶是 0.05wt%的环氧树脂的苯甲醇溶液， 粘结剂溶胶的涂布量为 0.001g/m2， 干燥除 去苯甲醇， 得到环氧树脂粘结剂层； 在环氧树脂粘结剂层上涂布由聚二甲基硅氧烷 与硅油组成的斥墨液， 聚二甲基硅氧烷与硅油的质量比为 5： 1， 斥墨液的涂布量为 5g/m2，干燥，使聚二甲基硅氧烷固化得到聚二甲基硅氧烷与硅油的混合物的斥墨层， 由此得到所述的喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 Ιμηι的聚乙烯薄膜的保护层。
将组成溶剂型制版墨水的 lwt%的聚丙烯酸树脂、 5wt%的三乙醇胺、 0.01wt%¾ 碱性艳兰 （颗粒粒径为 10nm) ， 及余量的乙二醇二甲醚混合， 室温搅拌混合液， 搅 拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型制版墨 水。 实施例 2
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 60wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法， 在该铝合金板表面涂布 粘结剂溶胶， 涂布的粘结剂溶胶是 15wt%的环氧树脂的苯甲醇溶液， 粘结剂溶胶的 涂布量为 10 g/m2， 干燥除去苯甲醇， 得到环氧树脂粘结剂层； 在环氧树脂粘结剂层 上涂布由聚甲基乙烯基硅氧烷与甲基硅油组成的斥墨液， 聚甲基乙烯基硅氧烷与甲 基硅油的质量比为 15： 1， 斥墨液的涂布量为 0.001g/m2， 干燥， 使聚甲基乙烯基硅 氧烷固化得到聚甲基乙烯基硅氧烷与硅油的混合物的斥墨层， 由此得到所述的喷墨 打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 20μηι的聚丙烯薄膜的保 护层。
将组成溶剂型制版墨水的 35wt%的酚醛树脂、 0.01^%的环氧当量值为 100克 / 当量的环氧树脂， 0.01wt%的黑色染料 SP (颗粒粒径为 3000nm) ， 及余量的乙二醇 单甲醚混合， 室温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及 杂质， 滤液为所述的溶剂型制版墨水。 实施例 3
将不经过电解砂目化和阳极氧化处理的工业用铝板用 5wt%稀氢氧化钠的水溶 液除油， 水洗后， 以旋涂的方法， 在该铝板表面涂布粘结剂溶胶， 涂布的粘结剂溶 胶是 0.05wt%的聚氨酯的二甲苯溶液， 粘结剂溶胶的涂布量为 1 g/m2， 干燥除去二甲 苯， 得到聚氨酯粘结剂层； 在聚氨酯粘结剂层上涂布由浓度为 20wt%的含氟异氰酸 酯树脂的二甲亚砜溶液组成的斥墨液， 斥墨液的涂布量为 5g/m2， 干燥除去二甲基亚 砜， 得到含氟异氰酸酯树脂的斥墨层， 由此得到所述的喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 ΙΟμηι的聚戊烯薄膜的保护层。
将组成溶剂型制版墨水的 20wt%的环氧树脂， 2^%的多异氰酸酯， 10^%的染 料酸性蓝 9 (颗粒粒径为 2000nm) ， 及余量的乙二醇单正丁醚混合， 室温搅拌混合 液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型 制版墨水。 实施例 4
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 40wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法， 在该铝合金板表面涂布 粘结剂溶胶， 涂布的粘结剂溶胶是 15wt%的聚氨酯的二甲苯溶液， 粘结剂溶胶的涂 布量为 2g/m2， 干燥除去二甲苯， 得到聚氨酯粘结剂层； 在聚氨酯粘结剂层上涂布由 浓度为 0.01wt%的含氟丙烯酸树脂的二甲苯溶液组成的斥墨液， 斥墨液的涂布量为 0.001g/m2, 干燥除去二甲苯， 得到含氟丙烯酸树脂的斥墨层， 由此得到所述的喷墨 打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 ΙΟμηι的聚乙二烯薄膜的 保护层。
将组成溶剂型制版墨水的 15wt%的聚酰亚胺树脂， 0.03wt%的三乙胺， 5^%的 活性黑 （颗粒直径在 30nm) ， 及余量的丙二醇甲醚醋酸酯混合， 室温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型制版 墨水。 实施例 5
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 30wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法， 在该铝合金板表面涂布 粘结剂溶胶，涂布的粘结剂溶胶是 0.05^%的聚苯乙烯的四氢呋喃溶液，粘结剂溶胶 的涂布量为 1.5g/m2， 干燥除去四氢呋喃， 得到聚苯乙烯粘结剂层； 在聚苯乙烯粘结 剂层上涂布由聚甲基苯基硅氧烷与月桂酸二丁基锡组成的斥墨液， 聚甲基苯基硅氧 烷与月桂酸二丁基锡的质量比为 6： 1， 斥墨液的涂布量为 2g/m2， 干燥， 使聚甲基 苯基硅氧烷固化得到聚甲基苯基硅氧烷与月桂酸二丁基锡的混合物的斥墨层， 由此 得到所述的喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 5μηι的 聚丙二烯薄膜的保护层。
将组成溶剂型制版墨水的 35^%的聚甲基丙烯酸树脂， 4wt%的三聚氰胺， lwt% 的 Ν,Ν—二甲基苯胺 （颗粒直径在 lOOnm) ， 及余量的乙二醇单乙醚混合； 室温搅 拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的 溶剂型制版墨水。 实施例 6
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 60wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 15wt%的聚苯乙烯的苯乙醇溶液， 粘结剂溶 胶的涂布量为 2.5g/m2， 干燥除去苯乙醇， 得到聚苯乙烯粘结剂层； 在聚苯乙烯粘结 剂层上涂布由聚甲基乙基硅氧烷与氨基硅烷组成的斥墨液， 聚甲基乙基硅氧烷与氨 基硅烷的质量比为 8： 1， 斥墨液的涂布量为 lg/m2， 干燥， 使聚甲基乙基硅氧烷固 化得到聚甲基乙基硅氧烷与氨基硅烷的混合物的斥墨层， 由此得 到所述的喷墨打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 12μηι的聚 乙烯醇薄膜的保护层。
将组成溶剂型制版墨水的 5^%的甲基硅树脂， 0.03wt%的双氰胺， 0.01%的硅油， lwt%的染料酸性黄 23 SF (颗粒直径在 lOOOnm) ， 及余量的丙二醇单甲醚混合； 室 温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所 述的溶剂型制版墨水。 实施例 7
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 40wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶，涂布的粘结剂溶胶是 0.05wt%的明胶的水溶液，粘结剂溶胶的涂布 量为 4g/m2， 干燥除去水， 得到明胶粘结剂层； 在明胶粘结剂层上涂布由浓度为 0.01wt%的含氟环氧树脂的醋酸丁酯溶液组成的斥墨液， 斥墨液的涂布量为 0.005g/m2, 干燥除去醋酸丁酯， 得到含氟环氧树脂的斥墨层， 由此得到所述的喷墨 打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 6μηι的聚乙烯醇縮丁醛 薄膜的保护层。
将组成溶剂型制版墨水的 5wt%的聚丙烯酸树脂与甲醇的反应产物（反应物投料 时， 聚丙烯酸： 甲醇的摩尔比为 1： 2)， 0.03^%的环氧当量值为 2000克 /当量的环 氧树脂， lwt%的碱性艳兰（颗粒直径在 2000nm) ， 及余量的丙二醇单乙醚混合； 室 温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所 述的溶剂型制版墨水。 实施例 8
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 50wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 15wt%的明胶的水溶液， 粘结剂溶胶的涂布 量为 1.5g/m2， 干燥除去水， 得到明胶粘结剂层； 在明胶粘结剂层上涂布由浓度为 20wt%的含氟聚乙烯树脂的乙二醇（40wt% )和丙二醇（40wt% )溶液组成的斥墨液， 斥墨液的涂布量为 3g/m2，干燥除去乙二醇和丙二醇，得到含氟聚乙烯树脂的斥墨层， 由此得到所述的喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 3μηι的聚苯乙烯薄膜的保护层。
将组成溶剂型制版墨水的 5wt%的聚甲基丙烯酸树脂与甲醇的反应产物（反应物 投料时， 聚甲基丙烯酸： 甲醇的摩尔比为 1： 2)， 0.03^%的环氧当量值为 100 克 / 当量的环氧树脂， lwt%的碱性艳兰（颗粒直径在 2000nm)， 及余量的丙二醇乙醚醋 酸酯混合； 室温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂 质， 滤液为所述的溶剂型制版墨水。 实施例 9
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 30wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶，涂布的粘结剂溶胶是 0.05wt%的醇酸树脂的乙醇溶液，粘结剂溶胶 的涂布量为 0.5g/m2， 干燥除去乙醇， 得到醇酸树脂粘结剂层； 在醇酸树脂粘结剂层 上涂布由聚甲基丙基硅氧烷与氨丙基硅烷组成的斥墨液， 聚甲基丙基硅氧烷与氨丙 基硅烷的质量比为 10： 1， 斥墨液的涂布量为 0.01g/m2， 干燥， 使聚甲基丙基硅氧烷 固化得到聚甲基丙基硅氧烷与氨丙基硅烷的混合物的斥墨层， 由此得到所述的喷墨 打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 16μηι的聚对苯二甲酸乙 二醇酯薄膜的保护层。
将组成溶剂型制版墨水的 20wt%的聚酯树脂， 0.02wt%的过氧化苯甲酰， 0.02wt 的黑色染料 SP (颗粒直径在 3000nm) ， 及余量的丙二醇丁醚醋酸酯混合； 室温搅 拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的 溶剂型制版墨水。 实施例 10
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 30wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 15wt%的醇酸树脂的乙醇溶液， 粘结剂溶胶 的涂布量为 0.02g/m2， 干燥除去乙醇， 得到醇酸树脂粘结剂层； 在醇酸树脂粘结剂 层上涂布由聚甲基环己基硅氧烷与月桂酸二丁基锡组成的斥墨液， 聚甲基环己基硅 氧烷与月桂酸二丁基锡的质量比为 12 : 1， 斥墨液的涂布量为 0.005g/m2， 干燥， 使 聚甲基环己基硅氧烷固化得到聚甲基环己基硅氧烷与月桂酸二丁基锡的混合物的斥 墨层， 由此得到所述的喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚 度在 9μηι的聚氯乙烯薄膜的保护层。
将组成溶剂型制版墨水的 20^%的橡胶， 0.02wt%的过氧化苯甲酰， 0.02Wt%的 黑色染料 SP (颗粒直径在 3000nm) ， 及余量的乙二醇丁醚醋酸酯混合； 室温搅拌 混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶 剂型制版墨水。 实施例 11
将不经过电解砂目化和阳极氧化处理的工业用铝板用 5wt%稀氢氧化钠的水溶 液除油， 水洗后， 以旋涂的方法涂布。 在该铝板表面涂布粘结剂溶胶， 涂布的粘结 剂溶胶是 0.05wt%的聚酯的二元酸酯溶液， 粘结剂溶胶的涂布量为 0.005g/m2， 干燥 除去二元酸酯，得到聚酯粘结剂层；在聚酯粘结剂层上涂布由浓度为 0.01wt%含氟丙 烯酸树脂的丁醇溶液组成的斥墨液， 斥墨液的涂布量为 4g/m2， 干燥除去丁醇， 得到 含氟丙烯酸树脂的斥墨层， 由此得到所述的喷墨打印直接制版的铝版材。 在所得铝 版材上进一步覆盖厚度在 8μηι的聚偏二氯乙烯薄膜的保护层。
将组成溶剂型制版墨水的 lwt%的聚苯乙烯， 4Wt%的 N-N-二甲基苯胺， 10wt% 的酸性蓝 9 (颗粒直径在 800nm) ， 及余量的 N， N-二甲基甲酰胺混合； 室温搅拌混 合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂 型制版墨水。 实施例 12
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 40wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 15wt%的聚酯的二元酸酯溶液， 粘结剂溶胶 的涂布量为 0.01g/m2， 干燥除去二元酸酯， 得到聚酯粘结剂层； 在聚酯粘结剂层上 涂布由浓度为 20wt%含氟环氧树脂的丙酮溶液组成的斥墨液， 斥墨液的涂布量为 0.2g/m2， 干燥除去丙酮， 得到含氟环氧树脂的斥墨层， 由此得到所述的喷墨打印直 接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 2μηι的聚对苯二甲酸乙二醇酯 薄膜的保护层。
将组成溶剂型制版墨水的 lwt%的聚酰胺， 4Wt%的 N-N-二甲基苯胺， 10Wt%的 酸性蓝 9 (颗粒直径在 800nm) ， 及余量的二氧六环混合； 室温搅拌混合液， 搅拌至 固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型制版墨水。 实施例 13 将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 45wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶，涂布的粘结剂溶胶是 0.05Wt%的聚乙烯醇的水溶液，粘结剂溶胶的 涂布量为 0.06g/m2， 干燥除去水， 得到聚乙烯醇粘结剂层； 在聚乙烯醇粘结剂层上 涂布由聚甲基异丁基硅氧烷与甲氧基硅烷组成的斥墨液， 聚甲基异丁基硅氧烷与甲 氧基硅烷的质量比为 9 : 1， 斥墨液的涂布量为 2.5g/m2， 干燥， 使聚甲基异丁基硅氧 烷固化得到聚甲基异丁基硅氧烷与甲氧基硅烷的混合物的斥墨层， 由此得到所述的 喷墨打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 13μηι的聚戊烯薄膜 的保护层。
将组成溶剂型制版墨水的 35wt%的聚丙烯酸树脂与戊醇的反应产物 （反应物投 料时， 聚丙烯酸树脂：戊醇的摩尔比为 1： 2)， 0.02wt%的二乙醇胺， 1^%的染料酸 性黄 23 SF (颗粒直径在 2000nm) ， 及余量的乙酸仲丁酯混合； 室温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型制版 墨水。 实施例 14
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 35wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 15Wt%的聚乙烯醇的水溶液， 粘结剂溶胶的 涂布量为 0.45g/m2， 干燥除去水， 得到聚乙烯醇粘结剂层； 在聚乙烯醇粘结剂层上 涂布由聚乙基乙烯基硅氧烷与乙氧基硅烷组成的斥墨液， 聚乙基乙烯基硅氧烷与乙 氧基硅烷的质量比为 7 : 1， 斥墨液的涂布量为 1.5g/m2， 干燥， 使聚乙基乙烯基硅氧 烷固化得到聚乙基乙烯基硅氧烷与乙氧基硅烷的混合物的斥墨层， 由此得到所述的 喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 Ιμηι的聚丙二烯薄 膜的保护层。
将组成溶剂型制版墨水的 35wt%的聚氯乙烯， 0.02wt%的二乙醇胺， lWt%的染 料酸性黄 23 SF (颗粒直径在 2000nm) ， 及余量的 A级矿精油混合； 室温搅拌混合 液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型 制版墨水。 实施例 15
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 60wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶，涂布的粘结剂溶胶是 0.05%的聚醋酸乙烯酯的乙苯溶液，粘结剂溶 胶的涂布量为 0.004g/m2， 干燥除去乙苯， 得到聚醋酸乙烯酯粘结剂层； 在聚醋酸乙 烯酯粘结剂层上涂布由浓度为 2(^1%的含氟异氰酸酯的氯仿溶液组成的斥墨液， 斥 墨液的涂布量为 0.5g/m2， 干燥除去氯仿， 得到含氟异氰酸酯的斥墨层， 由此得到所 述的喷墨打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 ΙΟμηι的聚苯乙 烯薄膜的保护层。
将组成溶剂型制版墨水的 20wt%的聚碳酸酯， 0.01^%的 N-N-二甲基苯胺，
0.01wt%的黑色染料 SP (颗粒直径在 3000nm) ， 及余量的 B级矿精油混合； 室温搅 拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的 溶剂型制版墨水。 实施例 16
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 30wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 15%的聚醋酸乙烯酯的乙苯溶液， 粘结剂溶 胶的涂布量为 9g/m2， 干燥除去乙苯， 得到聚醋酸乙烯酯粘结剂层； 在聚醋酸乙烯酯 粘结剂层上涂布由浓度为 0.01wt%的含氟聚乙烯的二甲基亚砜溶液组成的斥墨液，斥 墨液的涂布量为 3g/m2， 干燥除去二甲基亚砜， 得到含氟聚乙烯的斥墨层， 由此得到 所述的喷墨打印直接制版的铝版材。 在所得铝版材上进一步覆盖厚度在 5μηι的聚乙 烯醇縮丁醛薄膜的保护层。
将组成溶剂型制版墨水的 1^%的聚苯醚，0.01^%的 Ν-Ν-二甲基苯胺， 0.01wt% 的黑色染料 SP (颗粒直径在 3000nm) ， 及余量的乙二醇单甲醚混合； 室温搅拌混 合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂 型制版墨水。 实施例 17
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 32wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法， 在该铝合金板表面涂布 粘结剂溶胶， 涂布的粘结剂溶胶是 0.9wt%的聚乙烯醇縮丁醛的苯甲醇溶液， 粘结剂 溶胶的涂布量为 0.015g/m2， 干燥除去苯甲醇， 得到聚乙烯醇縮丁醛粘结剂层； 在聚 乙烯醇縮丁醛粘结剂层上涂布由聚二甲基硅氧烷与硅油组成的斥墨液， 聚二甲基硅 氧烷与硅油的质量比为 7： 1， 斥墨液的涂布量为 5g/m2， 干燥， 使聚二甲基硅氧烷 固化得到聚二甲基硅氧烷与硅油的混合物的斥墨层， 由此得到所述的喷墨打印直接 制版的铝版材。 在所得铝版材上进一步覆盖厚度在 Ιμηι的聚乙烯薄膜的保护层。
将组成溶剂型制版墨水的 5^%的聚氨酯树脂、 5wt%的三乙醇胺、 0.01^%的碱 性艳兰 （颗粒粒径为 10nm) ， 及余量的乙二醇二甲醚混合， 室温搅拌混合液， 搅拌 至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶剂型制版墨水。 实施例 18
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 50wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法， 在该铝合金板表面涂布 粘结剂溶胶， 涂布的粘结剂溶胶是 10wt%的聚酰胺的二甲苯溶液， 粘结剂溶胶的涂 布量为 6g/m2， 干燥除去二甲苯， 得到聚酰胺粘结剂层； 在聚酰胺粘结剂层上涂布由 聚甲基乙烯基硅氧烷与甲基硅油组成的斥墨液， 聚甲基乙烯基硅氧烷与甲基硅油的 质量比为 8 : 1， 斥墨液的涂布量为 0.001g/m2， 干燥， 使聚甲基乙烯基硅氧烷固化得 到聚甲基乙烯基硅氧烷与硅油的混合物的斥墨层， 由此得到所述的喷墨打印直接制 版的铝版材。 在所得铝版材上进一步覆盖厚度在 20μηι的聚丙烯薄膜的保护层。
将组成溶剂型制版墨水的 20wt%的醇酸树脂、 0.01^%的环氧当量值为 100克 / 当量的环氧树脂， 0.01wt%的黑色染料 SP (颗粒粒径为 3000nm) ， 及余量的乙二醇 单甲醚混合， 室温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及 杂质， 滤液为所述的溶剂型制版墨水。 实施例 19
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 45wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法， 在该铝合金板表面涂布 粘结剂溶胶， 涂布的粘结剂溶胶是 1.5wt%的松香树脂的环己烷溶液， 粘结剂溶胶的 涂布量为 1.2 g/m2， 干燥除去环己烷， 得到松香树脂粘结剂层； 在松香树脂粘结剂层 上涂布由浓度为 20wt%的含氟异氰酸酯树脂的二甲基亚砜溶液组成的斥墨液， 斥墨 液的涂布量为 5g/m2， 干燥除去二甲基亚砜， 得到含氟异氰酸酯树脂的斥墨层， 由此 得到所述的喷墨打印直接制版的铝版材。在所得铝版材上进一步覆盖厚度在 ΙΟμηι的 聚戊烯薄膜的保护层。
将组成溶剂型制版墨水的 15wt%的苯并噁嗪树脂， 2Wt%的多异氰酸酯， 10wt% 的染料酸性蓝 9 (颗粒粒径为 2000nm) ， 及余量的乙二醇单正丁醚混合， 室温搅拌 混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤液为所述的溶 剂型制版墨水。 实施例 20
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 40wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 以旋涂的方法涂布。 在该铝合金板表面 涂布粘结剂溶胶， 涂布的粘结剂溶胶是 3^%的苯乙烯 -丁二烯橡胶的庚烷溶液， 粘 结剂溶胶的涂布量为 0.04g/m2， 干燥除去庚烷， 得到苯乙烯-丁二烯橡胶粘结剂层； 在苯乙烯 -丁二烯橡胶粘结剂层上涂布由聚甲基环己基硅氧烷与月桂酸二丁基锡组成 的斥墨液，聚甲基环己基硅氧烷与月桂酸二丁基锡的质量比为 10： 1， 斥墨液的涂布 量为 0.01g/m2， 干燥， 使聚甲基环己基硅氧烷固化得到聚甲基环己基硅氧烷与月桂 酸二丁基锡的混合物的斥墨层， 由此得到所述的喷墨打印直接制版的铝版材。 在所 得铝版材上进一步覆盖厚度在 9μηι的聚氯乙烯薄膜的保护层。
将组成溶剂型制版墨水的 15wt%的聚砜、5^%的环氧当量值为 100克 /当量的环 氧树脂， 0.01wt%的黑色染料 SP (颗粒粒径为 3000nm) ， 及余量的乙二醇单甲醚混 合， 室温搅拌混合液， 搅拌至固体溶质全部溶解， 过滤除去未溶的颗粒及杂质， 滤 液为所述的溶剂型制版墨水。 分别利用喷墨打印机将上述实施例 1〜20制得的溶剂型制版墨水喷涂在各自实 施例中所得的喷墨打印直接制版的铝版材上 （去除保护层） 形成图像； 然后将喷涂 有所述制版墨水的铝版材经 90〜300°C烤版，使所述制版墨水在制版墨水中固化剂的 作用下交联固化， 将经上述处理后的铝版材上机印刷， 通过检测， 印版的印刷适性 优良且耐印力可达 100000张左右， 印版图文中线的分辨率可达 ΙΟμηι, 5〜95%的网 点可完整清晰。 实施例 21
利用喷墨打印机将 Blackjet墨水（SPECTRA、英国）喷涂在实施例 1-20中所得的 喷墨打印直接制版的铝版材上 （去除保护层） 形成图像； 然后将喷涂有所述制版墨 水的铝版材经 90〜300°C烤版，使所述制版墨水在制版墨水中固化剂的作用下交联固 化， 将经上述处理后的铝版材上机印刷， 通过检测， 印版的印刷适性优良且耐印力 可达 10000张左右， 印版图文中线的分辨率可达 20μηι， 10~90%的网点可完整清晰。
实施例 22
利用喷墨打印机将精工墨水 （SOLVENT INK, 日本） 喷涂在实施例 1-20中所得 的喷墨打印直接制版的铝版材上 （去除保护层） 形成图像； 然后将喷涂有所述制版 墨水的铝版材经 90〜300°C烤版，使所述制版墨水在制版墨水中固化剂的作用下交联 固化， 将经上述处理后的铝版材上机印刷， 通过检测， 印版的印刷适性优良且耐印 力可达 50000张左右，印版图文中线的分辨率可达 15μηι， 5~90%的网点可完整清晰。 对比例 1
经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 40wt% ) ( 1% 的盐酸水溶液中电解两次， 时间分别为 30秒； 在 15%的硫酸水溶液中阳极氧化 30 秒） 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 利用喷墨打印机将墨水 （SPT510, 中国） 喷涂上面形成图像； 然后将喷涂有所述制版墨水的铝版材经 90〜300°C烤版， 使所述制版墨水在制版墨水中固化剂的作用下交联固化， 将经上述处理后的铝版材 上机印刷， 通过检测， 印版的印刷适性优良且耐印力可达 10000张左右， 印版图文 中线的分辨率可达 30μηι， 15~85%的网点可完整清晰。 对比例 2
将不经过电解砂目化和阳极氧化处理的工业用铝合金板 （含二氧化硅 40wt% ) 用 5wt%稀氢氧化钠的水溶液除油， 水洗后， 利用喷墨打印机将墨水（P522-6, 中国） 喷涂上面形成图像； 然后将喷涂有所述制版墨水的铝版材经 90〜300°C烤版，使所述 制版墨水在制版墨水中固化剂的作用下交联固化， 将经上述处理后的铝版材上机印 刷， 通过检测， 印版的印刷适性优良且耐印力可达 200张左右， 印版图文中线的分 辨率仅达 900μηι。

Claims

权利要求书
1、 一种喷墨打印直接制版的版材， 其特征是： 所述的版材包括金属板材、 涂布 在所述金属板材的表面的粘结剂层、 以及涂布在粘接剂层上的斥墨层；
所述粘结剂层中的粘结剂选自环氧树脂、 聚氨酯、 聚烯烃、 聚酯、 苯乙烯 -丁二 烯橡胶、 明胶、 聚乙烯醇縮丁醛、 聚酰胺、 松香树脂、 聚乙烯醇、 醇酸树脂、 聚醋 酸乙烯酯所组成的组中的至少一种；
所述的斥墨层是硅橡胶与固化剂的混合物或是含氟树脂。
2、 根据权利要求 1所述的喷墨打印直接制版的版材， 其特征是： 所述的斥墨层 上覆盖有保护层， 该保护层为厚度在 1〜20μηι之间的聚合物薄膜；
所述聚合物薄膜的聚合物为聚乙烯、 聚丙烯、 聚戊烯、 聚乙二烯、 聚丙二烯、 聚乙烯醇、 聚乙烯醇縮丁醛、 聚苯乙烯、 聚对苯二甲酸乙二醇酯、 聚氯乙烯、 聚偏 二氯乙烯树脂中的至少一种。
3、 根据权利要求 1所述的喷墨打印直接制版的版材， 其特征是： 所述的粘结剂 层是涂布粘结剂溶胶并干燥后得到的， 其中， 涂布的粘结剂溶胶是由溶质与溶剂组 成， 粘结剂溶胶中的溶质的浓度为 0.05〜15wt%， 粘结剂溶胶的涂布量为 0.001〜 10g/m2, 所述溶质为所述粘合剂； 和 /或
所述的斥墨层是涂布硅橡胶与固化剂的混合液或涂布含氟树脂与有机溶剂的混 合液并干燥后得到的， 其中， 涂布的硅橡胶与固化剂的混合液中的硅橡胶与固化剂 的质量比为 5 : 1〜15： 1， 硅橡胶与固化剂的混合液的涂布量为 0.001〜5g/m2; 涂布 的含氟树脂与有机溶剂的混合液中的含氟树脂的含量为 0.01〜20wt%，含氟树脂与有 机溶剂的混合液的涂布量为 0.001〜5g/m2。
4、 根据权利要求 1或 3所述的喷墨打印直接制版的版材， 其特征是： 所述的聚 烯烃选自聚丙烯、 聚氯乙烯、 聚苯乙烯所组成的组中的至少一种；
所述的含氟树脂是含氟丙烯酸树脂、 含氟异氰酸酯树脂、 含氟环氧树脂、 含氟 聚烯烃树脂中的至少一种； 所述的硅橡胶为聚二甲基硅氧烷， 和 /或聚二甲基硅氧烷中一个或两个甲基被乙 烯基、 苯基、 2 碳原子数 6的烷基或卤代苯基取代的产物；
所述的固化剂是硅烷的衍生物和 /或金属的有机羧酸盐。
所述的有机溶剂为二甲基亚砜、 二甲苯、 醋酸丁酯、 乙二醇、 丙二醇、 丁醇、 丙酮、 氯仿所组成的组中的至少一种。
5、 根据权利要求 3所述的喷墨打印直接制版的版材， 其特征是： 所述的溶剂选 自水、 乙醇、 二元酸酯、 环己烷、 庚烷、 四氢呋喃、 芳香族溶剂所组成的组中的至 少一种。
6.根据权利要求 5所述的喷墨打印直接制版的版材， 其特征是： 所述的芳香族溶 剂选自苯甲醇、 苯乙醇、 二甲苯、 乙苯、 甲苯所组成的组中的至少一种。
7、 根据权利要求 1所述的喷墨打印直接制版的版材， 其特征是： 所述的金属板 材是铝板基， 或是合金板基。
8、 根据权利要求 7所述的喷墨打印直接制版的版材， 其特征是： 所述的合金板 基是含 30〜60wt%二氧化硅的二氧化硅与铝的合金板基， 或含 l〜3wt%锌的铝锌合 金板基， 或含 0.1〜lwt%铁的铝铁合金板基。
9、 一种喷墨打印方法， 该方法包括以喷墨打印的方式， 将图文信息通过制版墨 水打印在权利要求 1和 3-8中任意一项所述的版材上，将带有图文信息的版材上机印 刷， 得到印刷品。
10、 根据权利要求 9所述的喷墨 方法， 所述制版墨水为溶剂型制版墨水， 该溶剂型制版墨水含有：
成膜树脂 l〜35wt%
固化剂 0.01〜5wt%
纳米级或微米级染料 0.01〜10wt%
溶剂 所述的成膜树脂选自聚丙烯酸树脂、 聚甲基丙烯酸树脂、 聚丙烯酸树脂的酯化 物、 聚甲基丙烯酸树脂的酯化物、 聚酰亚胺树脂、 甲基硅树脂、 聚酯树脂、 环氧树 月旨、 酚醛树脂、 聚氨酯树脂、 苯并噁嗪树脂、 醇酸树脂、 橡胶、 聚酰胺、 聚氯乙烯、 聚苯乙烯、 聚碳酸酯、 聚苯醚、 聚砜所组成的组中的至少一种；
所述的固化剂选自硅油、 低分子量环氧树脂、 双氰胺、 三聚氰胺、 乙醇胺、 三 乙胺、 多异氰酸酯、 过氧化苯甲酰、 乙酸酐、 2-乙基咪唑、 2， 4-二甲基咪唑、 偏苯 四酸二酐、 N-N-二甲基苯胺所组成的组中的至少一种；
所述的纳米级或微米级染料的颗粒粒径为 10〜3000nm。
11、 根据权利要求 10所述的喷墨打印方法， 其特征是： 所述的聚丙烯酸树脂的 酯化物包括聚丙烯酸树脂与 1 碳原子数 5的一元醇的酯化反应产物； 所述的聚甲 基丙烯酸树脂的酯化物包括聚甲基丙烯酸树脂与 1 碳原子数 5的一元醇的酯化反 应产物；
所述的低分子量环氧树脂的环氧当量值为 100〜2000克 /当量。
12、根据权利要求 10所述的喷墨打印方法， 其特征是： 所述的制版墨水中的染料 选自酸性染料、 活性染料或碱性染料中的一种。
13、 根据权利要求 12所述的喷墨打印方法， 其特征是： 所述的酸性染料是染料 酸性蓝 9、 染料酸性蓝 9 SF、 染料酸性黄 23 SF中的一种；
所述的活性染料是黑色染料 SP系列或活性黑中的一种；
所述的碱性染料是蓝色染料中的碱性艳兰、 Ν,Ν-二甲基苯胺中的一种。
14、根据权利要求 10所述的喷墨打印方法， 其特征是： 所述的制版墨水中的溶 剂选自乙二醇单甲醚、 乙二醇单乙醚、 乙二醇单正丁醚、 乙二醇二甲醚、 丙二醇单 甲醚、 丙二醇单乙醚、 丙二醇甲醚醋酸酯、 丙二醇乙醚醋酸酯、 丙二醇丁醚醋酸酯、 乙二醇丁醚醋酸酯、 Ν， Ν-二甲基甲酰胺、 二氧六环、 乙酸仲丁酯、 Α级矿精油、 B 级矿精油中的一种。
PCT/CN2010/072239 2010-04-27 2010-04-27 喷墨打印直接制版的版材及喷墨打印方法 WO2011134142A1 (zh)

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