WO2012163288A1 - 用于纳米材料打印直接制版的墨水及其制备方法 - Google Patents

用于纳米材料打印直接制版的墨水及其制备方法 Download PDF

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Publication number
WO2012163288A1
WO2012163288A1 PCT/CN2012/076376 CN2012076376W WO2012163288A1 WO 2012163288 A1 WO2012163288 A1 WO 2012163288A1 CN 2012076376 W CN2012076376 W CN 2012076376W WO 2012163288 A1 WO2012163288 A1 WO 2012163288A1
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Prior art keywords
ink
resin
dye
group
printing
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PCT/CN2012/076376
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English (en)
French (fr)
Inventor
周海华
邝旻翾
宋延林
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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 EP12792281.3A priority Critical patent/EP2727970B1/en
Priority to JP2014513044A priority patent/JP5937203B2/ja
Priority to US14/123,508 priority patent/US9296909B2/en
Publication of WO2012163288A1 publication Critical patent/WO2012163288A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention belongs to ink for printing plate making, relates to material for direct printing of inkjet printing based on nano material, and particularly relates to ink which can be used for nano-print to plate (NTP) and a preparation method thereof.
  • NTP nano-print to plate
  • NTP nanomaterial printing direct plate making technology
  • the nano-material printing direct plate-making technology uses an inkjet printer (plate-making machine) to spray the plate-making ink on the surface of the plate to form a lipophilic image area, and the unpainted area is a hydrophilic non-image area, using the graphic area.
  • the contrast between the hydrophilic and oleophilic regions of the non-image area enables printing.
  • the nano-material printing direct plate-making technology avoids the post-processing process such as exposure and development, and the resolution and the printing durability of the obtained printing plate are better after printing.
  • the nano-material printing direct plate-making ink already has weak solvent and water-based plate-making ink, but the ink droplets will spread on the surface of the printing plate during printing, and the plate-making precision is lowered.
  • the invention aims to effectively suppress the ink droplet by adjusting the formulation composition. Diffusion behavior to improve plate making accuracy and print quality. Summary of the invention
  • One of the objects of the present invention is to provide an ink for direct printing technology of nano material printing which can improve plate making precision and print quality.
  • Another object of the present invention is to provide a method of preparing an ink for nanomaterial printing direct plate making technology.
  • the ink for direct plate making of nano material printing of the present invention is based on the total amount of ink, and the composition and content of the ink are:
  • the film-forming resin is at least one selected from the group consisting of a phenol resin, an epoxy resin, a polyurethane resin, an olefin resin, and a cyanate resin.
  • the phenol resin may be various commonly used phenol resins, preferably a thermoplastic phenol resin (i.e., a linear phenol resin).
  • the epoxy resin may be various epoxy resins commonly used in the art, and is not particularly limited.
  • the epoxy resin may be selected from the group consisting of a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, a linear aliphatic epoxy resin, and an aliphatic epoxy resin.
  • the polyurethane resin may be selected from various resins which are obtained by condensation of an isocyanate and a hydroxyl group-containing compound which are conventionally used in the art, and the isocyanate and the hydroxyl group-containing compound may be conventionally selected in the art, and are not particularly limited.
  • the isocyanate may be selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, methylcyclohexyl diisocyanate, and 1,4-cyclohexyl diisocyanate
  • the hydroxyl group-containing compound may be selected from poly Carbonate diols, polyether triols, polyether diols (such as polyoxypropylene diol, polytetrahydrofuran diol, polypropylene glycol, and polyethylene glycol), polyester diols, and polyacrylate polyols.
  • the vinyl resin is selected from the group consisting of acrylic resin, methacrylic resin, polyhydroxystyrene resin, polyvinyl butyral resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene chloride-vinyl chloride copolymer resin, chlorosulfonate At least one of the group consisting of a polyethylene resin, a chlorinated polypropylene resin, and the like.
  • the cyanate resin may be selected from a bisphenol A type cyanate resin, a dicyclopentadiene bisphenol type cyanate or a polydiisocyanate resin.
  • the particles of the nano- or micro-sized dye have a particle diameter of 10 to 3000 nm.
  • the dye is selected from a dye of any one of an acid dye, a reactive dye or a basic dye.
  • the dye preferably uses dye acid blue 9, dye acid blue 9 SF or dye acid yellow 23 SF in an acid dye; preferably one of black dye SP series or reactive black in reactive dye; preferably alkaline
  • the blue dye in the dye is selected from any one of basic brilliant blue, crystal violet, and Victoria blue.
  • the organic solvent is at least one selected from the group consisting of an alcohol solvent, an ester solvent, and an alcohol ether solvent.
  • the alcohol solvent is at least one selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, and butylene glycol.
  • the ester solvent is selected from the group consisting of methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, dimethyl carbonate, propylene carbonate and propylene glycol methyl ether acetate. At least one of the groups.
  • the alcohol ether solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether (for example, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether), ethylene glycol II At least one of the group consisting of methyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether.
  • the humectant is at least one selected from the group consisting of glycerin, propylene glycol, polyethylene glycol, xylitol, polypropylene glycol, hexanediol, sorbitol, and amino acid.
  • water may be a conventional choice in the art, preferably deionized water having an electrical conductivity of less than 10 microsiemens per centimeter.
  • the invention relates to a method for preparing an ink for direct printing of nano material printing: 5 ⁇ 30wt% of a film-forming resin, 0.01 ⁇ 5wt% of a nanometer or micron dye, 30 ⁇ based on the total amount of the ink 60 wt% of the organic solvent, 0.01 to 5 wt% of the humectant and the balance of water are stirred and mixed at room temperature (for example, 18-35 ° C) (preferably, the stirring time is 2 to 6 hours), after the film-forming resin is completely dissolved.
  • the impurities and/or insoluble matter in the mixed solution are removed by multistage filtration, and the obtained filtrate is the ink of the present invention.
  • the multi-stage filtration is to sequentially filter the mixed solution by using a sand core funnel and a microporous filter, and specifically, filtering and removing impurities and/or insoluble substances in the mixed solution by using a sand core funnel, and then adopting
  • the microporous membrane is filtered to further remove more minute impurities and/or insolubles in the mixed solution, and the obtained filtrate is the water-based ink of the present invention.
  • the filtration is carried out by using a sand core funnel.
  • the filtration scheme is firstly filtered using a glass sand core funnel (G1 type glass sand core funnel) having a pore diameter of 20 to 30 ⁇ m, and then a glass sand having a pore diameter of 3 to 4 ⁇ m is used.
  • the core funnel (G4 glass core funnel) was filtered.
  • the filtration method using a microporous membrane filter is preferably carried out by first filtering with a polytetrafluoroethylene microporous membrane having a pore diameter of 0.45 ⁇ m, and then using a polytetrafluoroethylene microporous membrane having a pore diameter of 0.22 ⁇ m. filter.
  • the ink for direct printing of nano material printing of the invention can be controlled by a computer controlled inkjet printer (such as
  • CTP7600 plate making system (see CN1800982A)) Spraying ink on the surface of the metal substrate to form the graphic area, and then curing the plate to obtain a printing plate that can be printed on the machine.
  • the resulting printing plate has a higher printing on the machine.
  • the printing durability (100,000 impressions), the resolution of printed images is better, can achieve dot reproduction rate of over 98% and resolution higher than 175 lpi, and at the same time reduce chemical pollution and post-processing process.
  • the curing treatment conditions may be various curing methods commonly used in the art, as long as the ink can be converted from a liquid state to a solid state, for example, the curing may be photocuring or thermal curing.
  • the conditions for curing in the present invention are also not particularly limited, and may be conventionally selected depending on the curing mode and the composition of the ink, and are not described herein again. detailed description
  • thermoplastic phenolic resin commercially available from Liaoning Xinggang Friction Material Co., Ltd., model 2123
  • 60% by weight of t-butanol 60% by weight of t-butanol
  • 0.01% by weight of propylene glycol 0.01% by weight of propylene glycol
  • dye acid blue 9 commercially available from Liaoning Xinggang Friction Material Co., Ltd., model 2123
  • the particle size of the particles 2000 nm) and the balance of deionized water, stirred and mixed at room temperature for 5 hours, and the mixture was filtered by a sand core funnel and a micron pore filter to remove undissolved particles and impurities, and the filtrate was obtained.
  • the mixture is sequentially filtered by a sand core funnel and a micron-diameter filter membrane by first filtering with a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m; and then using a polytetrafluoroethylene micropore having a pore diameter of 0.45 ⁇ m.
  • the filter is filtered.
  • thermoplastic phenolic resin commercially available from Liaoning Xinggang Friction Material Co., Ltd., model 2123
  • 30 wt% of tert-butanol 30 wt% of tert-butanol, 0.01 wt% of propylene glycol, and 0.01 wt% of black dye SP (according to 5% by weight of total ink)
  • the particle size of the particles 2000 nm
  • the balance of deionized water stirred and mixed at room temperature for 6 hours, and the mixture was filtered by a sand core funnel and a micron pore filter to remove undissolved particles and impurities, and the obtained filtrate was Ink for direct printing of nanomaterials.
  • the mixture is sequentially filtered by a sand core funnel and a micron-diameter filter membrane by first filtering with a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m; and then using a polytetrafluoroethylene micropore having a pore diameter of 0.45 ⁇ m.
  • the filter is filtered.
  • thermoplastic phenolic resin commercially available from Qingdao Dechen Chemical Co., Ltd., Model 2402, Shandong province
  • 50% by weight of t-butanol 50% by weight of t-butanol
  • 0.2% by weight of propylene glycol 50% by weight of t-butanol
  • black dye SP 50% by weight of black dye SP (according to a total of 15% by weight of ink)
  • the mixture is sequentially filtered by a sand core funnel and a micron-diameter filter membrane by first filtering with a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m; and then using a polytetrafluoroethylene micropore having a pore diameter of 0.45 ⁇ m.
  • the filter is filtered.
  • Epoxy resin (5 wt% of the total ink) (commercially available from Bosheng Resin Materials Trading Co., Ltd., Sanxiang Town, Zhongshan City, Guangdong province, model 815), 30 wt% isopropyl alcohol, 5 wt% glycerin, 0.01 wt% black Dye SP (particle size: 3000 nm) and the balance of deionized water, stir and mix at room temperature for 6 hours, and then filter the mixture with sand core funnel and micron pore filter to remove undissolved particles and impurities.
  • the filtrate is an ink for direct plate making of nanomaterial printing.
  • the mixture is sequentially filtered by a sand core funnel and a micron-diameter filter membrane by first filtering with a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m; and then using a polytetrafluoroethylene micropore having a pore diameter of 0.45 ⁇ m.
  • the filter is filtered.
  • the total amount of ink will account for 15 W t% of polyurethane (commercially available from Hebei Anping triple filter Equipment Co., Model No. 100), ⁇ 50% of dimethyl carbonate, 0.02 wt% of xylitol, 0.03% ⁇
  • the crystal violet (particle size: 10 nm) and the balance of deionized water were stirred and mixed at room temperature for 3 hours, and the mixture was filtered by a sand core funnel and a micron pore filter to remove undissolved particles and impurities.
  • the resulting filtrate is an ink for direct plate making of nanomaterial printing.
  • the mixture is sequentially filtered by a sand core funnel and a micron-diameter filter membrane by first filtering with a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m; and then using a polytetrafluoroethylene micropore having a pore diameter of 0.45 ⁇ m.
  • the filter is filtered.
  • Cyanate resin (commercially available from Liaoning Hongshan Chemical Co., Ltd., model JQ-5E), 40% ethanol, 0.03wt% polyethylene glycol (commercially available from 20% by weight of total ink) Jiangsu Sixin Interface Technology Co., Ltd., model PEG-600), 5% active black (particle size: 30nm) and the balance of deionized water, stirred at room temperature for 4 hours, using sand core The mixture is filtered through a funnel and a micron-diameter filter to remove undissolved particles and impurities, and the resulting filtrate is an ink for direct plate-making of nanomaterial printing.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; filtration was then carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m, followed by filtration using a polytetrafluoroethylene microporous membrane having a pore size of 0.22 ⁇ m.
  • Acrylic resin (commercially available from Changzhou Hanguang Coating Co., Ltd., Jiangsuzhou, model AR-2070), 30% by weight of ethyl acetate, 20% by weight of butyl acetate, 0.02% by weight of acrylic resin Propylene glycol (commercially available from Jiangsu Sixin Interface Technology Co., Ltd., model PPG-400), lwt% renovated (particle size: lOOnm) and the balance of deionized water, stirred at room temperature for 3 hours, The mixture was filtered by a sand core funnel and a microporous membrane filter in order to remove undissolved particles and impurities, and the obtained filtrate was an ink for direct printing of nano material printing.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; then filtration was carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m.
  • methacrylic resin commercially available from Jinan Yuanxiang Chemical Co., Ltd., Shandongzhou, model BC-201-805
  • 52wt3 ⁇ 4 ⁇ propylene glycol methyl ether acetate 0.04wt% hexanediol
  • Lwt% dye acid yellow 23 SF particle size: lOOOnm
  • the balance of deionized water stir and mix at room temperature for 2 hours, and then filter the mixture with sand core funnel and micron pore filter.
  • the dissolved particles and impurities, and the obtained filtrate is an ink for direct plate making of nano material printing.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; then filtration was carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m.
  • Polyhydroxystyrene resin (number average molecular weight: 2000), 60% by weight of propylene glycol methyl ether, 5% by weight of sorbitol, and 4% by weight of basic brilliant blue (particle diameter: 2000 nm)
  • the remaining amount of deionized water was stirred and mixed at room temperature for 5 hours, and the mixture was filtered by a sand core funnel and a micron pore filter to remove undissolved particles and impurities, and the obtained filtrate was used for direct printing of nano material printing. Ink.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; filtration was then carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m, followed by filtration using a polytetrafluoroethylene microporous membrane having a pore size of 0.22 ⁇ m.
  • Example 10 Example 10
  • a polyvinyl butyral resin (commercially available from Beijing Chemical Reagent Co., Ltd., viscosity at 25 ° C for 100 seconds), 54 wt% of propylene glycol monomethyl ether, and 3 wt% of polypropylene glycol (commercially available) Purchased from Jiangsu Sixin Interface Technology Co., Ltd., model PPG-600), 2wt% dye acid blue 9 SF (particle size: 500nm) and the balance of deionized water, stirred at room temperature for 4 hours, The mixture was filtered in turn with a sand core funnel and a microporous filter to remove undissolved particles and impurities, and the resulting filtrate was an ink for direct plate making of nanomaterial printing.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; then filtration was carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m.
  • a vinyl chloride-vinyl acetate copolymer resin (commercially available from Wuhanford Biochemical Co., Ltd.), 60% by weight of ethyl lactate, and 5% by weight of polyethylene glycol (commercially available from Jiangsu Sixin), which accounts for 30% by weight of the total ink.
  • Interface Agent Technology Co., Ltd., model PEG-800 2wt% black dye SP (particle size: 3000nm) and the balance of deionized water, stirred at room temperature for 4 hours, using sand core funnel and micron
  • the pore size filter filters the mixed solution to remove undissolved particles and impurities, and the obtained filtrate is an ink for direct plate making of nano material printing.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; filtration was then carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m, followed by filtration using a polytetrafluoroethylene microporous membrane having a pore size of 0.22 ⁇ m.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration; then filtering with a 0.45 ⁇ m pore size polytetrafluoroethylene microporous membrane followed by a pore size of 0.22 ⁇ m The polytetrafluoroethylene microporous membrane was filtered.
  • Chlorosulfonated polyethylene resin (commercially available from Jilin City Longyun Chemical Co., Ltd.), 44% by weight of ethyl formate, 4% by weight of xylitol, 2% by weight of acid blue 9
  • the particle size of the particles 800 nm
  • the balance of deionized water stirred and mixed at room temperature for 4 hours, and the mixture was filtered by a sand core funnel and a micron pore filter to remove undissolved particles and impurities, and the obtained filtrate was Ink for direct printing of nanomaterials.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; filtration was then carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m, followed by filtration using a polytetrafluoroethylene microporous membrane having a pore size of 0.22 ⁇ m.
  • Chlorinated polypropylene resin (commercially available from Guangzhou Suxing Chemical, model: EVA), 60% by weight of propylene glycol dimethyl ether, 0.03% by weight of hexanediol, 0.03% by weight of black dye SP, which will account for 20% by weight of the total ink (particle size: 900 nm) and the balance of deionized water, stirred at room temperature for 5 hours, and the mixture was filtered by a sand core funnel and a micron pore filter to remove undissolved particles and impurities. For direct printing of inks for nanomaterial printing.
  • the mixture is filtered by a sand core funnel and a micron-diameter filter membrane in sequence, and then filtered by a glass sand core funnel having a pore diameter of 20 to 30 ⁇ m, and then a glass sand core funnel having a pore diameter of 3 to 4 ⁇ m is used. Filtration was carried out; filtration was then carried out using a polytetrafluoroethylene microporous membrane having a pore size of 0.45 ⁇ m, followed by filtration using a polytetrafluoroethylene microporous membrane having a pore size of 0.22 ⁇ m.
  • the conductivity of the deionized water in the above embodiments 1 to 14 is less than 10 microsiemens/cm; the inks for direct printing of nanomaterials prepared by the above embodiments 1 to 14 are respectively sprayed by an inkjet printer.
  • the aluminum plate, zinc plate base or copper plate base of nano and micro structure then the aluminum plate base, zinc plate base or copper plate base coated with the above ink is heat-cured (curing temperature is 80-150 ° C, curing time) For 0.5-2 hours), the aluminum plate base, zinc plate base or copper plate base after the above curing treatment is respectively printed on the machine, and the printing plate has excellent printability and the printing durability can reach about 100,000 impressions.
  • the resolution of the image is up to 1751pi.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

一种可用于纳米材料打印直接制版技术的墨水及其制备方法。以所述墨水的总重为基准，将5-30wt%的成膜树脂、0.01-5wt%的纳米级或微米级染料、30-60wt%的有机溶剂、0.01-5wt%的保湿剂及余量的水在室温下搅泮混合，待成膜树脂完全溶解后，经多级过滤除去混合溶液中的杂质和/或不溶物，所得到的滤液即为墨水。墨水通过喷墨打印机喷涂在金属基材表面，形成打印图案，经固化处理后可直接上机印刷，减少了化学污染及后处理过程，印版的耐印力可达10万印，分辨率达1751pi。

Description

用于纳米材料打印直接制版的墨水及其制备方法 技术领域
本发明属于印刷制版用墨水，涉及基于纳米材料的喷墨打印直接制版用材料，特别 涉及可用于纳米材料打印直接制版技术 （Nano-print to Plate, 简称 NTP) 的墨水及其制 备方法。 背景技术
在数字成像领域喷墨打印技术作为传统印刷技术的重要组成部分正日益受到关注。 纳米材料打印直接制版技术 （NTP) 的流程为： 首先将图文信息处理后通过计算机传递 到喷墨打印机 （制版机） 上， 喷墨打印机将图文信息打印在已涂布涂层或只具有砂目、 不带有涂层的铝版基上， 图文部分由纳米复合转印材料组成， 上机印刷时亲油， 非图文 部分亲水， 通过亲油亲水的反差实现图文信息的转印。
纳米材料打印直接制版技术是利用喷墨打印机（制版机）将制版用墨水喷涂在版基 表面形成亲油的图文区域， 未喷涂墨水的区域为亲水的非图文区域， 利用图文区域与非 图文区域的亲水与亲油的反差实现印刷。 纳米材料打印直接制版技术避免了曝光、 显影 等后处理过程， 所得印版上机印刷后分辨率和耐印力较好。 目前纳米材料打印直接制版 用墨水已经有弱溶剂及水基制版墨水， 但打印时墨滴会在版基表面发生扩散， 使制版精 度下降， 本发明旨在通过调整配方组成， 有效抑制墨滴的扩散行为， 以提高制版精度及 印刷品质量。 发明内容
本发明的目的之一在于提供一种能够提高制版精度及印刷品质量的、用于纳米材料 打印直接制版技术的墨水。
本发明的目的之二是提供一种用于纳米材料打印直接制版技术的墨水的制备方法。 本发明的用于纳米材料打印直接制版的墨水， 以墨水的总量为基准， 该墨水的组分 及含量为：
成膜树脂 5〜30wt%
纳米级或微米级染料 0.01〜5wt%
有机溶剂 30〜60wt% 保湿剂 0.01〜5wt%
水 余量
所述的成膜树脂为选自酚醛树脂、 环氧树脂、 聚氨酯树脂、 烯类树脂和氰酸酯树脂 所组成的组中的至少一种。
所述的酚醛树脂可以为常用的各种酚醛树脂， 优选为热塑性酚醛树脂 （即， 线性酚 醛树脂）。
所述的环氧树脂可以为本领域常用的各种环氧树脂， 没有特别限定。 例如， 所述环 氧树脂可以选自缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、 缩水甘油胺类环氧树 脂、 线型脂肪族类环氧树脂和脂肪族类环氧树脂。
所述的聚氨酯树脂可以选自本领域常用的各种由异氰酸酯与含羟基的化合物缩合 而得到的树脂，所述异氰酸酯和含羟基化合物可以为本领域的常规选择，没有特别限定。 例如，所述异氰酸酯可以选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、对苯二异氰酸酯、 甲基环己基二异氰酸酯和 1,4-环己垸二异氰酸酯， 所述含羟基化合物可以选自聚碳酸酯 二醇、 聚醚三醇、 聚醚二醇 （如聚氧化丙烯二醇、 聚四氢呋喃二醇、 聚丙二醇和聚乙二 醇）、 聚酯二醇和聚丙烯酸酯多元醇。
所述的烯类树脂选自丙烯酸树脂、 甲基丙烯酸树脂、 聚羟基苯乙烯树脂、 聚乙烯醇 缩丁醛树脂、 氯乙烯-乙酸乙烯酯共聚树脂、 偏氯乙烯 -氯乙烯共聚树脂、 氯磺化聚乙烯 树脂和氯化聚丙烯树脂等所组成的组中的至少一种。
所述氰酸酯树脂可以选自双酚 A型氰酸酯树脂、 双环戊二烯双酚型氰酸酯或聚二异 氰酸酯树脂。
所述的纳米级或微米级染料的颗粒的粒径为 10〜3000nm。
所述的染料选自酸性染料、 活性染料或碱性染料中的任一种颜色的染料。
所述的染料优选使用酸性染料中的染料酸性蓝 9、 染料酸性蓝 9 SF或染料酸性黄 23 SF等；优选使用活性染料中的黑色染料 SP系列或活性黑中的一种；优选使用碱性染料中 的蓝色染料中选自碱性艳兰、 结晶紫和维多利亚兰的任何一种。
所述的有机溶剂选自醇类溶剂、 酯类溶剂和醇醚类溶剂所组成的组中的至少一种。 所述的醇类溶剂为选自乙醇、 正丙醇、 异丙醇、 正丁醇、 异丁醇、 叔丁醇、 乙二醇 和丁二醇等所组成的组中的至少一种。
所述的酯类溶剂为选自甲酸甲酯、 甲酸乙酯、 乙酸甲酯、 乙酸乙酯、 乙酸丁酯、 乳 酸乙酯、 碳酸二甲酯、 碳酸丙烯酯和丙二醇甲醚醋酸酯等所组成的组中的至少一种。 所述的醇醚类溶剂为选自乙二醇单甲醚、 乙二醇单乙醚、 乙二醇丁醚 （例如， 乙二 醇单丁醚、 乙二醇二丁醚）、 乙二醇二甲醚、 乙二醇二乙醚、 丙二醇单甲醚、 丙二醇单 乙醚、 丙二醇二甲醚和丙二醇二乙醚等所组成的组中的至少一种。
所述的保湿剂为选自甘油、 丙二醇、 聚乙二醇、 木糖醇、 聚丙二醇、 己二醇、 山 梨醇和氨基酸等所组成的组中的至少一种。
本发明中，水可以为本领域的常规选择，优选为电导率为小于 10微西门子 /厘米的 去离子水。
本发明的用于纳米材料打印直接制版的墨水的制备方法： 以所述墨水的总量为基 准， 将 5〜30wt%的成膜树脂、 0.01〜5wt%的纳米级或微米级染料、 30〜60wt%的有机溶 剂、 0.01〜5wt%的保湿剂及余量的水在室温 （例如： 18-35 °C ) 下搅拌混合 （优选搅拌 时间为 2〜6小时）， 待成膜树脂完全溶解后， 经多级过滤除去混合溶液中的杂质和 /或不 溶物， 所得到的滤液即为本发明所述的墨水。
所述的多级过滤优选是依次用砂芯漏斗和微米孔径的滤膜对混合溶液进行过滤，具 体而言，先用砂芯漏斗进行过滤除去混合溶液中的杂质和 /或不溶物，再采用微米孔径的 滤膜进行过滤进一步除去混合溶液中的更微小的杂质和 /或不溶物，所得到的滤液即为本 发明所述的水基墨水。
所述的采用砂芯漏斗进行过滤，优选过滤方案为先采用孔径为 20〜30微米的玻璃砂 芯漏斗（G1型玻璃砂芯漏斗）进行过滤后， 再采用孔径为 3〜4微米的玻璃砂芯漏斗（G4 型玻璃砂芯漏斗） 进行过滤。
所述的采用微米孔径的滤膜进行过滤， 优选方案为先采用孔径为 0.45微米的聚四氟 乙烯微孔滤膜进行过滤后， 再采用孔径为 0.22微米的聚四氟乙烯微孔滤膜进行过滤。
本发明的用于纳米材料打印直接制版的墨水，可通过计算机控制的喷墨打印机（如
CTP7600制版系统 （请参见 CN1800982A) ) 将墨水喷涂在金属基材表面上形成图文区 域， 然后将版基进行固化处理得到可以上机印刷的印版， 所得印版在上机印刷时具有较 高的耐印力 （耐印力达到 10万印张）， 印刷品图文的分辨率较好， 能够达到 98%以上的 网点再现率和高于 175 lpi的分辨率， 并同时减少了化学污染及后处理过程。
根据本发明， 所述固化处理的条件可以为本领域常用的各种固化方式， 只要能使 墨水由液态转变成固态即可， 例如： 所述固化可以为光固化， 也可以为热固化。 本发明 对于固化的条件也没有特别限定，可以根据固化方式的不同以及墨水的组成进行常规选 择， 本文不再赘述。 具体实施方式
实施例 1
将占墨水总量 30wt%的热塑性酚醛树脂 （商购自辽宁省星港摩擦材料有限公司， 型号为 2123)、 60wt%的叔丁醇、 0.01wt%的丙二醇、 5wt%的染料酸性蓝 9 (颗粒的粒径： 2000nm)及余量的去离子水， 在室温下搅拌混合 5小时， 依次用砂芯漏斗和微米孔径的 滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接制版 的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 3〜4 微米的玻璃砂芯漏斗进行过滤;然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过 滤。 实施例 2
将占墨水总量 5wt%的热塑性酚醛树脂（商购自辽宁省星港摩擦材料有限公司， 型 号为 2123)、 30wt%的叔丁醇、 0.01wt%的丙二醇、 0.01wt%的黑色染料 SP (颗粒的粒径： 2000nm)及余量的去离子水， 在室温下搅拌混合 6小时， 依次用砂芯漏斗和微米孔径的 滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接制版 的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 3〜4 微米的玻璃砂芯漏斗进行过滤;然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过 滤。 实施例 3
将占墨水总量 15wt%的热塑性酚醛树脂 （商购自山东省青岛德臣化工有限公司， 型号为 2402)、 50wt%的叔丁醇、 0.2wt%的丙二醇、 0.5wt%的黑色染料 SP (颗粒的粒径： lOOOnm)及余量的去离子水， 在室温下搅拌混合 4小时， 依次用砂芯漏斗和微米孔径的 滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接制版 的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 3〜4 微米的玻璃砂芯漏斗进行过滤;然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过 滤。 实施例 4
将占墨水总量 5wt%的环氧树脂（商购自广东省中山市三乡镇博锐树脂材料贸易商 行， 型号为 815)、 30wt%的异丙醇、 5wt%的甘油、 0.01wt%的黑色染料 SP (颗粒的粒 径： 3000nm)及余量去离子水， 在室温下搅拌混合 6小时， 依次用砂芯漏斗和微米孔径 的滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接制 版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 3〜4 微米的玻璃砂芯漏斗进行过滤;然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过 滤。
实施例 5
将占墨水总量 15Wt%的聚氨酯 （商购自河北省安平县三联过滤器材有限公司， 型 号为 100)、 50^%的碳酸二甲酯、 0.02wt%的木糖醇、 0.03^%的结晶紫 （颗粒的粒径： 10nm)及余量的去离子水， 在室温下搅拌混合 3小时， 依次用砂芯漏斗和微米孔径的滤 膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接制版的 墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 3〜4 微米的玻璃砂芯漏斗进行过滤;然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过 滤。 实施例 6
将占墨水总量 20wt%的氰酸酯树脂 （商购自辽宁省红山化工股份有限公司， 型号 为 JQ-5E)、 40^%的乙醇、 0.03wt%的聚乙二醇（商购自江苏四新界面剂科技有限公司， 型号为 PEG-600)、 5^%的活性黑 （颗粒的粒径： 30nm)及余量的去离子水， 在室温下 搅拌混合 4小时，依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤除去未溶的颗粒 及杂质， 所得滤液为用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤后， 再采用孔径为 0.22微米 的聚四氟乙烯微孔滤膜进行过滤。 实施例 7
将占墨水总量 25wt%的丙烯酸树脂 (商购自江苏省常州市汉光涂料有限公司， 型号 为 AR-2070)、 30wt%的乙酸乙酯、 20wt%的乙酸丁酯、 0.02wt%的聚丙二醇 （商购自江 苏四新界面剂科技有限公司， 型号为 PPG-400)、 lwt%的维多利亚兰 （颗粒的粒径： lOOnm) 及余量的去离子水， 在室温下搅拌混合 3小时， 依次用砂芯漏斗和微米孔径的 滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接制版 的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤。 实施例 8
将占墨水总量 18wt%的甲基丙烯酸树脂 （商购自山东省济南远祥化工有限公司， 型号为 BC-201-805)、 52wt¾^丙二醇甲醚醋酸酯、 0.04wt%的己二醇、 lwt%的染料酸 性黄 23 SF (颗粒的粒径： lOOOnm) 及余量的去离子水， 在室温下搅拌混合 2小时， 依 次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为 用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤。 实施例 9
将占墨水总量 30wt%的聚羟基苯乙烯树脂（数均分子量为 2000)、 60^%的丙二醇 甲醚、 5wt%的山梨醇、 4wt%的碱性艳兰 （颗粒的粒径： 2000nm) 及余量的去离子水， 在室温下搅拌混合 5小时，依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤除去未 溶的颗粒及杂质， 所得滤液为用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤后， 再采用孔径为 0.22微米 的聚四氟乙烯微孔滤膜进行过滤。 实施例 10
将占墨水总量 26^%的聚乙烯醇缩丁醛树脂 （商购自北京化学试剂公司， 25°C下 的粘度 100秒）、 54wt%的丙二醇单甲醚、 3wt%的聚丙二醇 （商购自江苏四新界面剂科 技有限公司， 型号为 PPG-600)、 2wt%的染料酸性蓝 9 SF (颗粒的粒径： 500nm) 及余 量的去离子水， 在室温下搅拌混合 4小时， 依次用砂芯漏斗和微米孔径的滤膜对混合液 进行过滤除去未溶的颗粒及杂质， 所得滤液为用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤。 实施例 11
将占墨水总量 30wt%的氯乙烯-乙酸乙烯酯共聚树脂 （商购自武汉福德生物化工有 限公司）、 60wt%的乳酸乙酯、 5wt%的聚乙二醇（商购自江苏四新界面剂科技有限公司， 型号为 PEG-800)、 2wt%的黑色染料 SP (颗粒的粒径： 3000nm) 及余量的去离子水， 在 室温下搅拌混合 4小时，依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤除去未溶 的颗粒及杂质， 所得滤液为用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45 微米的聚四氟乙烯微孔滤膜进行过滤后，再采用孔径为 0.22微米 的聚四氟乙烯微孔滤膜进行过滤。 实施例 12
将占墨水总量 25^%的偏氯乙烯-氯乙烯共聚树脂 （商购自潮北省武汉福德生物化 工有限公司）、 55^%的碳酸丙烯酯、 3wt%的丙三醇、 lwt%的黑色染料 SP (颗粒的粒 径： 2000nm)及余量的去离子水， 在室温下搅拌混合 3小时， 依次用砂芯漏斗和微米孔 径的滤膜对混合液进行过滤除去未溶的颗粒及杂质，所得滤液为用于纳米材料打印直接 制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤后， 再采用孔径为 0.22微米 的聚四氟乙烯微孔滤膜进行过滤。 实施例 13
将占墨水总量 26wt%的氯磺化聚乙烯树脂 （商购自吉林省吉林市龙运化工有限公 司）、 44wt%的甲酸乙酯、 4wt%的木糖醇、 2wt%的酸性蓝 9 (颗粒的粒径： 800nm) 及 余量的去离子水， 在室温下搅拌混合 4小时， 依次用砂芯漏斗和微米孔径的滤膜对混合 液进行过滤除去未溶的颗粒及杂质， 所得滤液为用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤后， 再采用孔径为 0.22微米 的聚四氟乙烯微孔滤膜进行过滤。 实施例 14
将占墨水总量 20wt%的氯化聚丙烯树脂（商购自广州粟星化工，型号： EVA)、60wt% 的丙二醇二甲醚、 0.03wt%的己二醇、 0.03wt%的黑色染料 SP (颗粒的粒径： 900nm) 及余量的去离子水， 在室温下搅拌混合 5小时， 依次用砂芯漏斗和微米孔径的滤膜对混 合液进行过滤除去未溶的颗粒及杂质， 所得滤液为用于纳米材料打印直接制版的墨水。
所述的依次用砂芯漏斗和微米孔径的滤膜对混合液进行过滤是先采用孔径为 20〜 30微米的玻璃砂芯漏斗进行过滤后，再采用孔径为 3〜4微米的玻璃砂芯漏斗进行过滤； 然后再用孔径为 0.45微米的聚四氟乙烯微孔滤膜进行过滤后， 再采用孔径为 0.22微米 的聚四氟乙烯微孔滤膜进行过滤。 上述实施例 1〜14中的去离子水的电导率均小于 10微西门子 /厘米；将上述实施例 1〜14制备得到的用于纳米材料打印直接制版的墨水， 分别利用喷墨打印机喷涂在具有 纳米及微米结构的铝版基、 锌版基或铜版基上， 然后将喷涂有上述墨水的铝版基、 锌版 基或铜版基进行热固化处理（固化温度为 80-150°C， 固化时间为 0.5-2小时）， 分别将经 上述固化处理后的铝版基、 锌版基或铜版基上机印刷， 通过检测， 印版的印刷适性优良 且耐印力可达 10万印左右， 图像的分辨率达 1751pi。

Claims

权利要求
1. 一种用于纳米材料打印直接制版的墨水， 其特征是， 以墨水的总量为基准， 所述 的墨水的组分及含量为：
成膜树脂 5〜30wt%
纳米级或微米级染料 0.01〜5wt%
有机溶剂 30〜60wt%
保湿剂 0.01〜5wt%
水
所述的成膜树脂为选自酚醛树脂、 环氧树脂、 聚氨酯树脂、 烯类树脂和氰酸酯树脂 所组成的组中的至少一种。
2. 根据权利要求 1所述的用于纳米材料打印直接制版的墨水， 其特征是： 所述的烯 类树脂为选自丙烯酸树脂、甲基丙烯酸树脂、聚羟基苯乙烯树脂、聚乙烯醇缩丁醛树脂、 氯乙烯-乙酸乙烯酯共聚树脂、 偏氯乙烯 -氯乙烯共聚树脂、 氯磺化聚乙烯树脂和氯化聚 丙烯树脂所组成的组中的至少一种。
3. 根据权利要求 1所述的用于纳米材料打印直接制版的墨水， 其特征是： 所述的纳 米级或微米级染料的颗粒的粒径为 10〜3000nm。
4. 根据权利要求 1或 3所述的用于纳米材料打印直接制版的墨水，其特征是：所述的 染料为选自酸性染料、 活性染料或碱性染料中的任一种颜色的染料。
5. 根据权利要求 4所述的用于纳米材料打印直接制版的墨水， 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或染料酸性黄 23 SF;
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、 结晶紫和维多利亚兰中的一种。
6. 根据权利要求 1所述的用于纳米材料打印直接制版的墨水， 其特征是： 所述的有 机溶剂选自醇类溶剂、 酯类溶剂和醇醚类溶剂所组成的组中的至少一种。
7. 根据权利要求 6所述的用于纳米材料打印直接制版的墨水， 其特征是： 所述的醇 类溶剂为选自乙醇、 正丙醇、 异丙醇、 正丁醇、 异丁醇、 叔丁醇、 乙二醇和丁二醇所组 成的组中的至少一种；
所述的酯类溶剂为选自甲酸甲酯、 甲酸乙酯、 乙酸甲酯、 乙酸乙酯、 乙酸丁酯、 乳 酸乙酯、 碳酸二甲酯、 碳酸丙烯酯和丙二醇甲醚醋酸酯所组成的组中的至少一种； 所述的醇醚类溶剂为选自乙二醇单甲醚、 乙二醇单乙醚、 乙二醇丁醚、 乙二醇二甲 醚、 乙二醇二乙醚、 丙二醇单甲醚、 丙二醇单乙醚、 丙二醇二甲醚和丙二醇二乙醚所组 成的组中的至少一种。
8. 根据权利要求 1所述的用于纳米材料打印直接制版的墨水， 其特征是： 所述的保 湿剂为选自甘油、 丙二醇、 聚乙二醇、 木糖醇、 聚丙二醇、 己二醇、 山梨醇和氨基酸所 组成的组中的至少一种。
9. 一种根据权利要求 1〜8中任意一项所述的用于纳米材料打印直接制版的墨水的 制备方法， 其特征是， 以所述墨水的总量为基准， 将 5〜30wt%的成膜树脂、 0.01〜5wt% 的纳米级或微米级染料、 30〜60wt%的有机溶剂、 0.01〜5wt%的保湿剂及余量的水在室 温下搅拌混合， 待成膜树脂完全溶解后， 经多级过滤， 所得到的滤液为所述的墨水。
10. 根据权利要求 9所述的制备方法， 其特征是： 所述多级过滤是依次用砂芯漏斗 和微米孔径的滤膜对混合液进行过滤。
PCT/CN2012/076376 2011-06-02 2012-06-01 用于纳米材料打印直接制版的墨水及其制备方法 WO2012163288A1 (zh)

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