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WO2018166465A1 - 一种喷墨打印制备大面积结构生色图案的方法及基于结构色变化的防伪方法 - Google Patents

一种喷墨打印制备大面积结构生色图案的方法及基于结构色变化的防伪方法 Download PDF

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Publication number
WO2018166465A1
WO2018166465A1 PCT/CN2018/078942 CN2018078942W WO2018166465A1 WO 2018166465 A1 WO2018166465 A1 WO 2018166465A1 CN 2018078942 W CN2018078942 W CN 2018078942W WO 2018166465 A1 WO2018166465 A1 WO 2018166465A1
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Prior art keywords
pattern
content
ink
structural color
paper
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Ceased
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PCT/CN2018/078942
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English (en)
French (fr)
Inventor
武素丽
常杰
刘宝琦
张淑芬
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Dalian University of Technology
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Dalian University of Technology
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Publication date
Priority claimed from CN201710155140.XA external-priority patent/CN106891634B/zh
Priority claimed from CN201710153541.1A external-priority patent/CN107020853A/zh
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to US16/494,665 priority Critical patent/US11091661B2/en
Publication of WO2018166465A1 publication Critical patent/WO2018166465A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • 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
    • C09D11/322—Pigment inks
    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/02—Material of vegetable origin
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security 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
    • B41M5/0023—Digital printing methods characterised by the inks used

Definitions

  • the invention belongs to the field of large-area structural color pattern preparation and anti-counterfeiting, and particularly relates to a method for obtaining a large-area structural chromatic color pattern on paper by using an inkjet printing technology and an anti-counterfeiting method based on structural color change.
  • the color effect produced by the dispersion, refraction, diffraction, and interference of light is called a structural color.
  • the structural color has the characteristics and advantages of brightness, high saturation, and never fading. Therefore, how to prepare large-area structural color photonic crystal patterns in recent years has received great attention.
  • methods for obtaining structural color patterns include self-assembly methods, vertical deposition methods, spin coating methods, and inkjet printing techniques.
  • the self-assembly method requires the use of a patterned template substrate to assemble colloidal particles onto the template under the action of space confinement, which is difficult to prepare on a large scale, and limits the practical application of the patterned photonic crystal.
  • the vertical deposition method is based on the reflow force and capillary force in the evaporation process of latex particles to achieve latex particle assembly, and is the most commonly used method for colloidal crystal preparation.
  • the preparation requirements for large-area samples are still not satisfactory, and the spin coating method is used for large-area preparation of colloidal crystals.
  • this method requires dispersing the monodisperse latex sample in a high-viscosity dispersion, and the process of the redispersion process is very cumbersome, and it is sometimes difficult to find a suitable dispersion system.
  • the inkjet printing technology is more convenient for direct writing of large-area complex patterns and patterning of composite functional materials, and is simple in preparation and low in cost, and does not require the use of pre-patterned templates.
  • the structural color pattern printed by the inkjet printing technology can uniformly deposit the ink on the surface of the substrate, so that the large-area structural color pattern obtained is uniform in color.
  • the invention utilizes the characteristics of high refractive index microspheres, and can obtain a bright structural color by short-range order and long-range disorder assembly, and can print structural color patterns on various papers through a common commercial printer.
  • the structural color pattern can be applied to the field of anti-counterfeiting.
  • the methods for realizing anti-counterfeiting by using structural colors mainly include two types: one is etching technology to prepare responsive polymer film, and the anti-counterfeiting is realized by external stimulation; the other is by inkjet deposition.
  • the monodisperse nanoparticles are deposited on a pretreated glass, polydimethylsiloxane or the like matrix material.
  • the former has a complicated preparation process, and the prepared anti-counterfeit pattern has a mobile phase inside, which limits its use (Advanced Functional Materials, 2014, 24(41): 6430-6438.), which uses expensive printing equipment and requires matrix materials.
  • After pre-processing, it is necessary to achieve anti-counterfeiting by changing the background or the intensity of the light source Chemistry–An Asian Journal, 2016, 11(19): 2680-2685.).
  • the invention utilizes high refractive microspheres to print a pattern of structural colors by inkjet printing technology, and uses microspheres of different particle sizes to have the same color of the main body, and prints different color parts of the pattern with microsphere inks having different particle diameters.
  • the structure is bright, and a bright structural color pattern can be observed.
  • the brightness of the structural color is lowered, and the body color of the material is reflected at this time.
  • the pattern is hidden, thereby enabling the hiding and display of the structural color pattern only by observing the angle. Since the pattern hiding and display process does not require external stimulation, and the structural color itself has no phase change, the security pattern has the characteristics of simple preparation, strong practical durability.
  • the object of the present invention is to provide a simple and universal method for preparing large-area structural color patterns and an anti-counterfeiting method, which can obtain large-area structural color patterns of different colors on a paper without pretreatment by using an ordinary ink jet printer.
  • the method is not only low in cost, but also the substrate material used does not need to be pretreated, and the printed pattern exists in a solid form for ease of use.
  • the process of realizing the anti-counterfeiting does not require an external force to be applied to the pattern, and deformation does not occur because the microstructure does not change. Therefore, this method is practical.
  • a technical solution adopted by the present invention is: loading ink containing high refractive index monodisperse microspheres into an ink cartridge, designing a pattern by computer software, and uniformly depositing ink on the paper by using an inkjet printer. Large area structure color pattern. The hiding and display of the structural color pattern is achieved by changing the viewing angle.
  • the implementation process includes the following process steps:
  • the two designed patterns were printed on the paper by one inkjet printing technique to obtain a large-area structural color pattern.
  • the high boiling point auxiliary is an organic solvent having a boiling point of more than 180 °C.
  • the high refractive index monodisperse submicron colloidal microspheres in step 1 are nanospheres having a refractive index greater than 2, cadmium sulfide (CdS), cuprous oxide (Cu 2 O), titanium dioxide. (TiO 2 ), one of zinc sulfide (ZnS) or zinc oxide (ZnO).
  • the monodisperse colloidal microspheres in the step 1 have a particle size ranging from 90 to 400 nm.
  • the nano microspheres of different particle diameters are respectively arranged as ink, and different portions of the pattern are printed with different inks.
  • the monodisperse colloidal microspheres, the high boiling point auxiliary agent, the ethanol, the glycerin, the surfactant, the defoaming agent, the adhesive, the pH adjuster and the deionized water are mixed in the step 1.
  • the content of the monodisperse colloidal microspheres in the ink obtained by ultrasonic dispersion is 5 to 20 wt%
  • the content of the high boiling point auxiliary is 5 to 15 wt%
  • the content of ethanol is 8 to 20 wt%
  • the content of glycerin is 1 to 5 wt%
  • the surface The content of the active agent is 2 to 5 wt%
  • the content of the antifoaming agent is 0.1 to 0.2 wt%
  • the content of the adhesive is 1 to 4 wt%
  • the content of the pH adjuster is 2 to 4 wt%
  • the balance is deionized water. .
  • the high boiling point auxiliary in the step 1 is ethylene glycol, diethylene glycol or formamide.
  • the surfactant in the step 1 is OP-10 or polyvinylpyrrolidone.
  • the antifoaming agent in the step 1 is tributyl phosphate.
  • the adhesive in the step 1 is one of polyvinyl alcohol, a polyurethane resin and an acrylic resin.
  • the pH adjusting agent described in the step 1 is one of triethanolamine, diethanolamine and ethanolamine.
  • the paper described in the step 1 is one of a coated paper, an RC photographic paper, and a glossy photo paper.
  • the printer in the step 3 is an inkjet printer.
  • the pattern is a common pattern designed by computer software and a fast response matrix code.
  • the invention utilizes a common ink jet printer to uniformly deposit ink containing different particle diameters and monodisperse microspheres on the paper, so that the nanoparticles are arranged and assembled to obtain a short-range ordered, long-range disordered microstructure, such a microstructure passes through with the light.
  • the interaction the beautiful structural color, the change of the viewing angle, the change of the brightness of the structural color, and thus the hiding and display of the pattern, has greater practicability in anti-counterfeiting and information encryption.
  • the method is not only low in cost, but also the matrix material used does not need to be pretreated, and the method is practical.
  • a, b, and c are respectively a digital photograph, a scanning electron microscope image, and a reflection spectrum diagram of a green structure color pattern of a large area of inkjet printing in Example 2.
  • Figure 3a is a hidden digital photo of the pattern in Embodiment 3, the entire pattern is all yellow;
  • Figure 3b is a digital photograph of the display of the pattern in Embodiment 3, the butterfly in the upper left corner is red, the butterfly in the lower right corner is green, and the rest are yellow;
  • 4c-d are digital photographs of the quick response matrix code in the embodiment 4, c can observe the red two-dimensional code, the rest is yellow; the d image observes the green two-dimensional code, and the rest Part is yellow.
  • PVP polyvinylpyrrolidone powder
  • the content of the monodisperse colloidal microspheres is 12 wt%
  • the content of ethylene glycol is 5 wt%
  • the content of ethanol is 10 wt%
  • the content of glycerol is 5 wt.
  • the content of %, PVP was 2.7 wt%
  • the content of tributyl phosphate was 0.1 wt%
  • the content of polyvinyl alcohol was 1 wt%
  • the content of triethanolamine was 3 wt%
  • the balance was deionized water. Ultrasound for 30 min, formulated into a uniformly dispersed ink.
  • the configured ink is placed in the ink cartridge, and the designed pattern is printed by the inkjet printer, so that the CdS nanoparticles in the ink are uniformly deposited on the high gloss photographic paper, and the short-range ordered, long-range disordered microstructure is obtained, as shown in the figure. As shown in Fig. 1, a large area of red structural color pattern is finally obtained.
  • PVP polyvinylpyrrolidone powder
  • the content of the monodisperse colloidal microspheres is 15 wt%
  • the content of ethylene glycol is 5 wt%
  • the content of ethanol is 10 wt%
  • the content of glycerin is 5 wt%.
  • the content of PVP is 3 wt%
  • the content of tributyl phosphate is 0.1 wt%
  • the content of polyvinyl alcohol is 1.5 wt%
  • the content of triethanolamine is 3 wt%
  • the balance is deionized water. Ultrasound for 30 min, formulated into a uniformly dispersed ink.
  • the configured ink is placed in the ink cartridge, and the designed pattern is printed by the inkjet printer, so that the CdS nanoparticles in the ink are uniformly deposited on the glossy photo paper, as shown in FIG. 2, and finally a large area of green structural color is obtained. pattern.
  • PVP polyvinylpyrrolidone powder
  • PVP polyvinylpyrrolidone powder
  • the ink is prepared: the content of the monodisperse colloidal microspheres is 15 wt%, the content of ethylene glycol is 5 wt%, the content of ethanol is 10 wt%, the content of glycerin is 5 wt%, the content of PVP is 3 wt%, and tributyl phosphate
  • the content of the ester was 0.1% by weight, the content of polyvinyl alcohol was 1.5% by weight, the content of triethanolamine was 3% by weight, and the balance was deionized water.
  • Ultrasonic 30min formulated into a uniform dispersion of ink, respectively, into three ink cartridges.
  • the ink is printed on the glossy photo paper by an inkjet printer under the experimental conditions of room temperature, and finally a large-area, different-color structural color pattern is obtained, as shown in FIG. 3 (wherein the background color utilizes CdS nanoparticles with a particle diameter of 290 nm).
  • the prepared ink is printed, and the orange-yellow structural color can be obtained.
  • the closer the observation angle is to the normal incidence the more obvious the contrast between the structural color of the two butterflies and the structural color of the background is, and a pattern with three bright structural colors can be observed;
  • the observation angle deviates from the normal incidence angle (>30°)
  • the structural color of the butterfly and the background is covered by its body color, and the body colors of the three are similar, both are yellow.
  • the color contrast between the butterfly and the background is low, and the butterfly is Hidden inside the background pattern.
  • Example 3 Using the ink of Example 3, a fast response matrix code with background was generated by computer software design, and it was printed on glossy photo paper by an inkjet printer, and a large-area pattern having two structural colors was obtained. As shown in FIG. 4, the closer the observation angle is to the normal incidence, the more obvious the color contrast of the matrix code and the background is, and the two bright structural colors can be observed while scanning the matrix code and obtaining the link. Obtaining a fast response matrix code that can be hidden and displayed, and when a bright structural color can be observed, the matrix code can be scanned and linked; when the viewing angle deviates from the normal incidence angle (>30°), the matrix code and the structural color of the background It is covered by the body color of both, and the body colors of the two are similar, both are yellow. At this time, the matrix code is hidden in the background pattern, and the matrix code cannot be scanned because of the low contrast between the two.
  • a certain amount of polyvinylpyrrolidone was placed in a 250 mL three-necked flask, and 75 mL of deionized water was added thereto, and the mixture was slowly stirred and warmed.
  • 0.01 mol of thioacetamide was added to the system, stirred for 10 min to make it evenly mixed, and then 100 ⁇ L of concentrated nitric acid was added thereto.
  • 0.02 mol of Zn (NO 3 ) was further added.
  • 6H 2 O was placed in a 5 mL aqueous solution, added to a three-necked flask, and the rotation speed was immediately increased so that the two were uniformly mixed.
  • the configured ink is placed in the ink cartridge, and the designed pattern is printed by the inkjet printer, so that the ZnS nanoparticles in the ink are uniformly deposited on the RC paper, and finally a large-area red structural color pattern is obtained.

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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)
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Abstract

一种喷墨打印制备大面积结构生色图案的方法、由该方法得到的结构生色图案及基于结构色变化的防伪方法。利用喷墨打印机将含有高折射率单分散胶体微球的分散液打印在纸张上，纳米微球在纸张上排列组装得到短程有序、长程无序的微观结构，该结构与光相互作用，可以观察到亮丽的结构色，实现图案的显示，改变观察角度，结构色亮度变化，实现图案的隐藏与显示。该方法简单方便，扩展性强，不需外界刺激，实现大面积结构色的制备及防伪。

Description

一种喷墨打印制备大面积结构生色图案的方法及基于结构色变化的防伪方法 技术领域
本发明属于大面积结构色图案制备及防伪领域，特别涉及一种利用喷墨打印技术在纸上得到大面积结构生色图案的方法及基于结构色变化的防伪方法。
背景技术
通过光的色散、折射、衍射、干涉而产生的颜色效应称为结构色。结构色具有光亮度、高饱和度、永不褪色等特点与优势，所以，近些年如何制备大面积的结构色光子晶体图案受到人们极大的关注。目前，得到结构色图案的方法包括自组装法、垂直沉积法、旋转涂层法和喷墨打印技术。自组装方法需要使用图案化的模板基底,在空间限域作用下组装胶体粒子到模板上,难以大规模制备,限制了图案化光子晶体的实际应用。垂直沉积方法是基于乳胶粒蒸发过程中的回流力及毛细力实现乳胶粒组装，是迄今为止胶体晶体制备的最为常用的方法。但仍不能满足对大面积样品的制备需求，为此旋转涂层方法被用于胶体晶体的大面积制备。但该方法需要将单分散胶乳样品分散在高黏度分散液中，其再分散过程的工艺非常繁琐，且有时很难找到合适的分散体系。而喷墨打印技术更容易实现大面积复杂图案的直接书写和复合功能材料的图案化，且制备简便，成本低廉，无需使用预先图案化的模板。另外，喷墨打印技术打印的结构色图案可以使墨水均匀沉积在基质表面，从而使得到的大面积结构色图案颜色均一。
对于喷墨打印技术制备大面积结构色光子晶体图案，人们一般使用两类设备，一类是普通的喷墨打印机，另外一类就是材料喷墨沉积仪。前者价格低廉，打印的基质一般选择PET，墨水的材料包括聚合物微球(Journal of Materials Chemistry,2009,19(31):5499-5502.)、TiO 2(ACS nano,2016,10(3):3078-3086.)等。材料喷墨沉积仪相对于普通喷墨打印机价格昂贵，使其应用受到限制。宋延林等利用材料喷印沉积仪将聚合物微球打印在疏水的PDMS基质上(Advanced Optical Materials,2014,2(1):34-38.)。利用液滴在基底表面上三相线的滑移抑制“咖啡环”效应，制备具有较大高径比且纳米粒子紧密堆积的组装结构，进而得到角度无关的结构色图案。
以上两种方法虽然能够得到结构色图案，但两种方法所需基质材料大都为塑料基质，而且需要经过预先处理，且第二种设备价格昂贵，限制了其使用。因此仍然有必要开发一种利用普通喷墨打印机在纸上打印得到大面积结构色图案的方法。本发明利用高折射率微球的特点，短程有序、长程无序组装即可得到亮丽的结构色，可通过普 通商用打印机，在多种纸张上打印结构色图案。
结构色图案可应用于防伪领域，目前，利用结构色实现防伪的方法主要包括两类：一类是刻蚀技术制备响应性聚合物膜，通过外界刺激实现防伪；另一类是通过喷墨沉积仪将单分散纳米粒子沉积在预处理过的玻璃、聚二甲基硅氧烷等基质材料上。前者制备工艺复杂，且制备的防伪图案内部为流动相，限制了其使用(Advanced Functional Materials,2014,24(41):6430-6438.)，后者使用的打印设备价格昂贵，且基质材料需要经过预处理，另外要通过改变背景或者光源强度才能够实现防伪(Chemistry–An Asian Journal,2016,11(19):2680-2685.)。
本发明利用高折射微球，通过喷墨打印技术打印结构色的图案，利用不同粒径的微球具有相同的本体色的特点，用含有不同粒径的微球墨水打印图案的不同颜色部位，当观察角度与入射光角度相接近时，结构色艳丽，可以观察到亮丽的结构色图案，而当观察角度与入射光角度偏离时，结构色的亮度降低，此时体现材料的本体色，此时图案被隐藏，进而实现仅仅通过观察角度的变化结构色图案的隐藏与显示。由于图案隐藏与显示过程中无须外界刺激、结构色本身没有相态的变化，所以该防伪图案具有制备简单、实用耐久性强的特点。
发明内容
本发明的目的是提供一种简单普适的制备大面积结构色图案的方法及防伪方法，利用普通喷墨打印机在无需预处理的纸上得到大面积不同颜色的结构色图案，当观察角度变化时，通过本体色和结构色之间的变化实现防伪。该方法不仅成本低廉，同时使用的基质材料不需要经过预处理，打印出来的图案以固态形式存在，便于使用。另外，实现防伪的过程不需要对图案施加外力，不会发生形变，因为微观结构不会发生改变。故此方法实用性强。
为解决上述技术问题，本发明采用的一个技术方案是：将含有高折射率单分散微球的墨水装于墨盒内，通过计算机软件设计图案，利用喷墨打印机使墨水在纸上均匀沉积，得到大面积的结构色图案。通过改变观察角度实现结构色图案的隐藏与显示。其实现过程包含以下工艺步骤：
①制备单分散胶体微球，将由单分散胶体微球、高沸点助剂、乙醇、甘油、表面活性剂、消泡剂、胶黏剂、pH调节剂和去离子水混合，超声分散得到的墨水装于喷墨打印机的墨盒中；
②通过计算机软件设计图案；
③将②所设计的图案用①所配制的墨水通过喷墨打印技术打印在纸上，得到大面积结构色图案。
所述高沸点助剂为沸点大于180℃的有机溶剂。
进一步地，在上述技术方案中，步骤①中所述高折射率单分散亚微米胶体微球为折射率大于2的纳米微球，硫化镉(CdS)，氧化亚铜(Cu 2O)，二氧化钛(TiO 2)，硫化锌(ZnS)或氧化锌(ZnO)中的一种。
进一步地，在上述技术方案中，步骤①中所述单分散胶体微球粒径范围为90～400nm。
进一步地，在上述技术方案中，将不同粒径的纳米微球分别配置成墨水，图案的不同部位用不同的墨水进行打印。
进一步地，在上述技术方案中，当观察角度与入射光角度接近时，可以观察到亮丽的结构色图案，当观察角度与入射光角度偏离时，结构色图案消失。
进一步地，在上述技术方案中，步骤①中所述单分散胶体微球、高沸点助剂、乙醇、甘油、表面活性剂、消泡剂、胶黏剂、pH调节剂和去离子水混合，超声分散得到的墨水中单分散胶体微球的含量为5～20wt％、高沸点助剂的含量为5～15wt％、乙醇的含量为8～20wt％、甘油的含量为1～5wt％、表面活性剂的含量为2～5wt％、消泡剂的含量为0.1～0.2wt％，胶黏剂的含量为1～4wt％，pH调节剂的含量为2～4wt％，余量为去离子水。
进一步地，在上述技术方案中，步骤①中所述高沸点助剂为乙二醇、二乙二醇或甲酰胺。
进一步地，在上述技术方案中，步骤①中所述表面活性剂为OP-10或聚乙烯吡咯烷酮。
进一步地，在上述技术方案中，步骤①中所述消泡剂为磷酸三丁酯。
进一步地，在上述技术方案中，步骤①中所述胶黏剂为聚乙烯醇、聚氨酯树脂和丙烯酸树酯中的一种。
进一步地，在上述技术方案中，步骤①中所述的pH调节剂为三乙醇胺、二乙醇胺和乙醇胺中的一种。
进一步地，在上述技术方案中，步骤①中所述的纸为铜版纸、RC相纸和高光相纸中的一种。
进一步地，在上述技术方案中，步骤③中所述打印机为喷墨打印机。
进一步地，在上述技术方案中，所述图案为计算机软件设计的普通图案和快速响应矩阵码。
发明有益效果
本发明利用普通喷墨打印机，使得含有不同粒径、单分散微球的墨水在纸上均匀沉积，使纳米粒子排列组装得到短程有序、长程无序的微观结构，这样的微观结构通过与光的相互作用，得到亮丽的结构色，改变观察角度，结构色的亮度发生变化，进而实现图案的隐藏与显示，在防伪和信息加密方面具有较大的实用性。该方法不仅成本低廉，同时使用的基质材料不需要经过预处理，方法实用性强。
附图说明
图1中a，b，c分别为实施例1中喷墨打印大面积的红色结构色图案的数码照片图、扫描电镜图以及反射光谱图；
图2中a，b，c分别为实施例2中喷墨打印大面积的绿色结构色图案的数码照片图、扫描电镜图以及反射光谱图。
图3a为实施例3中图案的隐藏数码照片图，整个图案全部为黄色；
图3b为实施例3中图案的显示数码照片图，左上角的蝴蝶为红色，右下角的蝴蝶为绿色，其余部分均为黄色；
图4a-b为实施例4中快速响应矩阵码的隐藏时的数码照片图，整个图案全部为黄色；
图4c-d为实施例4中快速响应矩阵码的显示时的数码照片图，c图可以观察到红色的二维码，其余部分是黄色；d图观察到的是绿色的二维码，其余部分是黄色。
具体实施方式
下面结合附图对本发明中的较佳实施例进行阐述，使本发明能够更好地被本领域技术研究人员理解，从而对本发明的保护范围做出清晰明确的界定。
实施例1
喷墨打印CdS墨水得到大面积的红色结构色图案.
首先制备单分散CdS胶体微球，具体制备方法如下：
称取5g聚乙烯吡咯烷酮粉末(PVP)，加入150mL二乙二醇，再加入等物质的量的硝酸镉和硫脲粉末，硝酸镉和硫脲的物质的量为20mmol，搅拌至所有粉末完全溶解。将溶液加热至160℃，保温反应5h后自然冷却至室温，将产物离心后乙醇和水洗3次干燥。得到单分散的、平均粒径为335nm的CdS纳米粒子。
称取一定量上述单分散CdS微球粉末，充分研磨，其中，加入单分散胶体微球的含量为12wt％、乙二醇的含量为5wt％、乙醇的含量为10wt％、甘油的含量为5wt％、PVP的含量为2.7wt％、磷酸三丁酯的含量为0.1wt％，聚乙烯醇的含量为1wt％，三乙醇胺的含量为3wt％，余量为去离子水。超声30min，配制成分散均匀的墨水。
将配置好的墨水装于墨盒内，利用喷墨打印机打印已经设计好的图案，使墨水中的CdS纳米粒子在高光相纸上均匀沉积，得到短程有序、长程无序的微观结构，如图1所示，最终得到大面积的红色结构色图案。
实施例2
喷墨打印CdS墨水得到大面积的绿色结构色图案.
首先制备单分散CdS胶体微球，具体制备方法如下：
称取5g聚乙烯吡咯烷酮粉末(PVP)，加入150mL二乙二醇，再加入等物质的量的硝酸镉和硫脲粉末，硝酸镉和硫脲的物质的量为15mmol，搅拌至所有粉末完全溶解。将溶液加热至162℃，保温反应6h后自然冷却至室温，将产物离心后乙醇和水洗3次干燥。得到单分散的、平均粒径为270nm的CdS纳米粒子。
称取一定量单分散CdS微球粉末，充分研磨，其中，加入单分散胶体微球的含量为15wt％、乙二醇的含量为5wt％、乙醇的含量为10wt％、甘油的含量为5wt％、PVP的含量为3wt％、磷酸三丁酯的含量为0.1wt％，聚乙烯醇的含量为1.5wt％，三乙醇胺的含量为3wt％，余量为去离子水。超声30min，配制成分散均匀的墨水。
将配置好的墨水装于墨盒内，利用喷墨打印机打印已经设计好的图案，使墨水中的CdS纳米粒子在高光相纸上均匀沉积，如图2所示，最终得到大面积的绿色结构色图案。
实施例3
大面积结构色图案的制备及基于结构色亮度变化的图案的隐藏与显示。
首先制备不同粒径、单分散的CdS胶体微球，具体制备方法如下：
称取5g聚乙烯吡咯烷酮粉末(PVP)，加入150mL二乙二醇溶液内，再加入摩尔比为1的硝酸镉和硫脲粉末，搅拌至所有粉末完全溶解。将溶液加热至150～160℃，保温反应5h后自然冷却至室温，将产物离心后用乙醇和水洗3次，干燥研磨。得到粒径为270nm的CdS粉末。
称取4.5g聚乙烯吡咯烷酮粉末(PVP)，加入150mL二乙二醇溶液内，再加入摩尔比为1的硝酸镉和硫脲粉末，搅拌至所有粉末完全溶解。将溶液加热至150～160 ℃，保温反应5h后自然冷却至室温，将产物离心后用乙醇和水洗3次，干燥研磨。得到粒径为290nm的CdS粉末。
称取5g聚乙烯吡咯烷酮粉末(PVP)，加入150mL二乙二醇溶液内，再加入摩尔比为1的硝酸镉和硫脲粉末，搅拌至所有粉末完全溶解。将溶液加热至150～160℃，保温反应5h后自然冷却至室温，将产物离心后用乙醇和水洗3次，干燥研磨。得到粒径为335nm的CdS粉末。
分别称取一定量上述三种粒径的单分散CdS微球粉末，充分研磨，分别配置墨水，打印图案的不同部位。其中，墨水配制：加入单分散胶体微球的含量为15wt％、乙二醇的含量为5wt％、乙醇的含量为10wt％、甘油的含量为5wt％、PVP的含量为3wt％、磷酸三丁酯的含量为0.1wt％，聚乙烯醇的含量为1.5wt％，三乙醇胺的含量为3wt％，余量为去离子水。超声30min，配制成分散均匀的墨水，分别装入三个墨盒内。通过计算机软件设计出带有两只蝴蝶的图案，将计算机与打印机相连。
利用喷墨打印机将墨水打印在高光相纸上，实验条件为室温，最终得到大面积、不同颜色的结构色图案，如图3所示，(其中，背景色利用粒径为290nm的CdS纳米粒子配制的墨水打印，可以得到橙黄色的结构色)观察角度越接近于垂直入射时，发现两只蝴蝶的结构色与背景的结构色对比度越明显，可以观察到具有三种亮丽结构色的图案；观察角度偏离垂直入射角度时(﹥30°)，蝴蝶与背景的结构色被其本体色掩盖，而三者的本体色相近，均为黄色，此时蝴蝶与背景的颜色对比度较低，蝴蝶被隐藏于背景图案内。
实施例4
基于结构色亮度变化的快速响应矩阵码的防伪应用。
使用实施例3中的墨水，通过计算机软件设计生成一个带有背景的快速响应矩阵码，利用喷墨打印机将其在高光相纸上打印，可以得到大面积的、具有两种结构色的图案。如图4所示，观察角度越接近于垂直入射时，发现矩阵码与背景的颜色对比度越明显，可以观察到两种亮丽结构色的同时也可以扫描此矩阵码并且得到链接。得到可隐藏可显示的快速响应矩阵码，并且当可以观察到亮丽结构色时，该矩阵码可以扫描并且得到链接；观察角度偏离垂直入射角度时(﹥30°)，矩阵码与背景的结构色被两者的本体色掩盖，而两者的本体色相近，均为黄色，此时矩阵码隐藏于背景图案内观察不到，且由于两者的对比度低，矩阵码无法扫描。
实施例5
喷墨打印ZnS墨水得到大面积的红色结构色图案.
首先制备单分散ZnS胶体微球，具体制备方法如下：
取一定量的聚乙烯吡咯烷酮置于250mL三口烧瓶中，向其中加入75mL的去离子水，缓慢搅拌升温。当温度达到80℃后，向体系内加入0.01mol的硫代乙酰胺，搅拌10min使其混合均匀，再向其中加入100μL的浓硝酸，反应10min后，再将0.02mol的Zn(NO 3)·6H 2O配置成5mL的水溶液，加入三口烧瓶中，立即增加转速，使得两者混合均匀，几分钟后将转速降低至500rpm，75℃下回流反应3h。将得到的产物用去离子水洗涤3-4遍，得到单分散的、平均粒径为230nm的ZnS纳米粒子。离心、真空干燥后待用。
称取一定量单分散ZnS微球粉末，充分研磨，其中，加入单分散胶体微球的含量为10wt％、甲酰胺的含量为10wt％、乙醇的含量为10wt％、甘油的含量为2wt％、PVP的含量为2wt％、磷酸三丁酯的含量为0.1wt％，聚乙烯醇的含量为1wt％，三乙醇胺的含量为2wt％，余量为去离子水。超声30min，配制成分散均匀的墨水。
将配置好的墨水装于墨盒内，利用喷墨打印机打印已经设计好的图案，使墨水中的ZnS纳米粒子在RC相纸上均匀沉积，最终得到大面积的红色结构色图案。

Claims (11)

  1. 一种喷墨打印制备大面积结构生色图案的方法，其特征在于，该方法包括如下工艺步骤：
    ①制备单分散胶体微球，将高折射率单分散胶体微球、高沸点助剂、乙醇、甘油、表面活性剂、消泡剂、胶黏剂、pH调节剂和去离子水混合，超声分散混合均匀，得到的稳定混合液作为墨水装于喷墨打印机的墨盒中；
    ②通过计算机软件设计图案；
    ③将②所设计的图案用①所配制的墨水通过喷墨打印技术打印在纸上，得到大面积结构色图案；
    所述高折射率单分散胶体微球为折射率大于2的单分散胶体微球；
    所述高沸点助剂为沸点大于180℃的有机溶剂。
  2. 根据权利要求1所述的方法，其特征在于，所述高折射率单分散胶体微球选自硫化镉，氧化亚铜，二氧化钛，硫化锌或氧化锌中的一种，所述的单分散胶体微球的粒径为90nm～400nm。
  3. 根据权利要求1所述的方法，其特征在于，所述高折射率单分散胶体微球、高沸点助剂、乙醇、甘油、表面活性剂、消泡剂、胶黏剂、pH调节剂和去离子水混合，超声分散得到的墨水中单分散胶体微球的含量为5～20wt％、高沸点助剂的含量为5～15wt％、乙醇的含量为8～20wt％、甘油的含量为1～5wt％、表面活性剂的含量为2～5wt％、消泡剂的含量为0.1～0.2wt％，胶黏剂的含量为1～4wt％，pH调节剂的含量为2～4wt％，余量为去离子水。
  4. 根据权利要求1所述的方法，其特征在于，所述高沸点助剂选自乙二醇、二乙二醇或甲酰胺。
  5. 根据权利要求1所述的方法，其特征在于，所述表面活性剂选自OP-10或聚乙烯吡咯烷酮。
  6. 根据权利要求1所述的方法，其特征在于，所述消泡剂选自磷酸三丁酯。
  7. 根据权利要求1所述的方法，其特征在于，所述胶黏剂选自聚乙烯醇、聚氨酯树脂和丙烯酸树酯中的一种。
  8. 根据权利要求1所述的方法，其特征在于，所述的pH调节剂选自三乙醇胺、二乙醇胺或乙醇胺中的一种。
  9. 根据权利要求1所述的方法，其特征在于，所述的纸选自铜版纸、RC相纸和高光相纸中的一种。
  10. 由权利要求1所述方法通过喷墨打印技术在纸上得到大面积的结构生色图案。
  11. 将权利要求1所述方法得到的大面积结构生色图案用于防伪的方法，其特征在于配置不同种类和/或不同粒径的胶体微球分散液作为不同颜色的墨水，图案的不同颜色部分采用不同的墨水打印。
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