CN113771520B - Structural color thermal sensitive paper based on thermochromic photonic crystals and preparation and application thereof - Google Patents

Structural color thermal sensitive paper based on thermochromic photonic crystals and preparation and application thereof Download PDF

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CN113771520B
CN113771520B CN202110895233.2A CN202110895233A CN113771520B CN 113771520 B CN113771520 B CN 113771520B CN 202110895233 A CN202110895233 A CN 202110895233A CN 113771520 B CN113771520 B CN 113771520B
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thermal
film
photonic crystal
paper
color
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CN113771520A (en
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葛建平
张欣
冉玉梅
傅茜茜
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East China Normal University
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East China Normal University
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    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/48—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/06—Polystyrene
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
    • G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/32—Thermal receivers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers

Abstract

The invention discloses structural color thermal sensitive paper based on a thermochromic photonic crystal. The principle of thermochromism and thermal printing is that under the heating condition, a thermal phase-change material is melted into liquid and permeates into pores among colloidal particles in photonic crystals to cause the increase of refractive index and the change of structural color, so that the thermal printing of patterns is realized. By adjusting the size of the colloidal particles, photonic crystal thermal sensitive paper with different colors can be prepared, and various color combinations among pattern backgrounds can be realized. The paper is compatible with commercial thermal printers, and the effects of high-resolution printing and gray scale printing are realized on the structural color thermal paper. Compared with the existing thermal sensitive paper, the thermal sensitive paper based on the thermochromic photonic crystals does not contain any dye, and the components are environment-friendly and harmless to human bodies; in view of the color generation principle of the structural color, the printed pattern is stable in color development and resistant to irradiation and not easy to fade.

Description

Structural color thermal sensitive paper based on thermochromic photonic crystals and preparation and application thereof
Technical Field
The invention belongs to the technical field of application and printing of colloidal photonic crystals, and relates to structural color thermal sensitive paper based on thermochromic photonic crystals, and preparation and application thereof.
Background
Thermal paper, or thermal recording paper, is coated process paper prepared by coating a thermo-sensitive coloring layer on plain paper. Under the heating condition, the leuco dye and the color developing agent in the color layer are subjected to chemical color development reaction, the dye is changed from colorless to colored, and the printing of characters or patterns can be realized by combining the precise heating of the printing head. Compared with common paper, the printing of patterns and characters on the thermal paper does not need the support of auxiliary equipment such as an ink box or a selenium drum, and the convenient and fast printing can be realized at any time and any place. Such paper has been widely used in shopping tickets, merchandise labels, and the like.
At present, the main disadvantages of the thermal paper are that: the color development mode is chemical reaction color development, and the reaction can be carried out reversibly under illumination, so that the printed patterns or characters are easy to fade and disappear under illumination; in addition, chemical dyes in the thermo-sensitive coloring layer and bisphenol A which is a commonly used color developing agent interfere with the endocrine system of human body and are harmful to the human body.
The structural color is stable in color development and environment-friendly in component, and the structural color is derived from the interaction between the photonic crystal structure which is periodically arranged and light. Compared with the traditional chemical dye, the structural color is only related to the microscopic physical structure of the dye, the generation of the color does not involve the use of any dye, and the dye is non-toxic and harmless and is expected to be applied to thermal printing, but the related technology is not reported.
Disclosure of Invention
In order to overcome the defects of common dye type thermal sensitive paper and utilize the advantages of structural color of photonic crystals, the invention provides structural color thermal sensitive paper based on thermochromic photonic crystals, which is of a double-layer structure and consists of a thermal phase change material layer and a solid photonic crystal layer (the thermal sensitive paper consists of a thermal phase change material and a solid photonic crystal and is packaged between two substrates).
And the thermal phase-change material is coated on the lower surface of the transparent protective layer.
Wherein the transparent protective layer is selected from one or more of polypropylene film, nylon film, polyester film, polyvinyl chloride film, polyethylene film and the like; preferably, it is a polyester film.
The thermal phase change material is selected from one or more of polyethylene glycol, polyvinyl alcohol, paraffin, ethylene-vinyl acetate copolymer, heneicosane, forty alkyl, octadecanol, icosane and other long-chain fatty alcohols; preferably, it is polyethylene glycol.
Wherein the solid photonic crystal is coated on the upper surface of the substrate.
Wherein the base material is selected from one or more of black, white or transparent polypropylene film, nylon film, polyester film, polyethylene film, polyvinyl chloride film, coated paper, paperboard, glass, epoxy resin film and the like; preferably a black polyester film.
Wherein the solid photonic crystal layer contains colloidal particles, and the colloidal particles, namely assembly elements of the colloidal particles are selected from one or more of polystyrene, silicon dioxide, hollow silicon dioxide, zinc sulfide, zinc oxide, titanium dioxide, cerium oxide, ferroferric oxide, polymethyl methacrylate, tin oxide, copper oxide, hollow phenolic resin and the like with uniform sizes; preferably, it is silica.
Wherein the size of the colloidal particles is 100-400nm; preferably, it is 200-300nm.
When the thermal phase change material is heated, the thermal phase change material is converted from a solid state into a liquid state and permeates into the colloidal particle gap of the photonic crystal layer, so that the refractive index is increased, and color change can be generated.
Wherein the thickness of the solid-state photonic crystal layer should be less than 20 μm, preferably 10 μm.
Wherein, the thickness of the thermal phase change material layer is more than 30% of the thickness of the solid-state photonic crystal layer and less than 25 μm, and preferably 3-10 μm.
The color change principle of the thermal paper is as follows: under the heating condition, the thermal phase-change material is melted into liquid and permeates into the colloidal particle gap of the solid photonic crystal, and the refractive index of the photonic crystal layer is increased, so that the color change is generated. By regulating the size of the colloidal particles of the photonic crystal layer, the photonic crystal structure color thermal sensitive paper with different colors can be prepared. Then, the existing commercial thermal printer can be used for carrying out accurate regional heating on the photonic crystal thermal paper, thereby realizing the visual effects of high-resolution printing and gray scale printing. Compared with the existing thermal sensitive paper, the structural color thermal sensitive paper based on the thermochromic photonic crystals provided by the invention does not relate to the use of any organic dye, and the components are environment-friendly and harmless to human bodies; meanwhile, the printed patterns are rich in color, stable in structural color development and resistant to irradiation, and the thermal sensitive paper is brand new.
The invention also provides application of the structural color thermal sensitive paper based on the thermochromic photonic crystals in gray scale printing and high resolution printing of pattern and characters in a commercial thermal printer, heating of directly written thermal sensitive paper and the like.
The invention also provides a preparation method of the structural color thermal sensitive paper based on the thermochromic photonic crystals, which comprises the following steps:
(1) And coating the supersaturated solution containing the colloidal particles on a substrate, and heating to volatilize the solvent to obtain the solid photonic crystal film.
(2) And heating the thermal phase-change material to be molten at the temperature higher than the phase-change temperature, uniformly coating the molten thermal phase-change material on the transparent protective layer, and re-solidifying the molten thermal phase-change material to obtain the thermal phase-change film.
(3) And (3) enabling the front surfaces of the photonic crystal film and the thermal phase change film to be opposite, and attaching the two layers of films along the edges by using a viscous material to obtain the photonic crystal structure color thermal sensitive paper.
In the step (1), the supersaturated solution containing colloidal particles is colloidal particle dispersion liquid obtained by ultrasonic dispersion of colloidal particles with the volume fraction of 20% -50% and a solvent with the volume fraction of 50% -80%; preferably, the colloidal solution is obtained by ultrasonic dispersion of 40% by volume of colloidal particles and 60% by volume of ethylene glycol.
Wherein the solvent is selected from one or more of water, glycol, ethanol, dimethyl sulfoxide, dimethyl formamide, propylene carbonate, methanol, propanol, butanol and the like; preferably, it is ethylene glycol.
In the step (1), the base material is one or more of a black, white or transparent polypropylene film, a nylon film, a polyester film, a polyethylene film, a polyvinyl chloride film, coated paper, paperboard, glass, an epoxy resin film and the like; preferably, it is a black polyester film.
In the step (1), the colloidal particles are one or more of polystyrene, silicon dioxide, hollow silicon dioxide, zinc sulfide, zinc oxide, titanium dioxide, cerium oxide, ferroferric oxide, polymethyl methacrylate, tin oxide, copper oxide, hollow phenolic resin and the like with uniform sizes; preferably, silica gel particles;
the size of the colloidal particles is 100-400nm; preferably, it is from 200nm to 300nm.
The purpose of heating in step (1): the solvent was evaporated to give a solid film.
In the step (1), the heating temperature is 60-100 ℃; preferably, it is 90 ℃.
In the step (1), the heating time is 10-60 minutes; preferably, it is 30 minutes.
In the step (2), the protective layer is one or more of a transparent polypropylene film, a nylon film, a polyester film, a polyethylene film, a polyvinyl chloride film and the like; preferably a transparent polyester film.
In the step (2), the thermal phase change material is one or more of polyethylene glycol, polyvinyl alcohol, paraffin, ethylene-vinyl acetate copolymer, heneicosane, forty-alkyl, octadecanol, icosane and other long-chain fatty alcohols; preferably, it is polyethylene glycol.
In the step (3), the two thin films are assembled together, that is, the base material is arranged on the outer side and serves as a protective layer, the photonic crystal layer is opposite to the front surface of the thermal phase change layer, the edges of the photonic crystal layer are fixed by using an adhesive material, and the double-layer structure is packaged between the base materials.
In the step (3), the viscous substance can be various glues or double-sided tapes; preferably a double sided tape.
Compared with the prior thermosensitive paper based on dye color change, the invention has the beneficial effects that:
the thermal sensitive paper prepared by combining the thermal phase change material and the photonic crystal structure color has no report so far. The thermochromic process of the structural color thermal sensitive paper does not involve any chemical reaction, the color is only related to the structure, and the structural color thermal sensitive paper is stable and does not fade under illumination. The structural color thermal sensitive paper does not contain any chemical dye, and the material is environment-friendly and pollution-free and is harmless to human bodies.
Drawings
In FIG. 1, a is a schematic diagram of the principle of color change of a photonic crystal structure color thermal sensitive paper; b-c and d-e are SEM sectional views of the thermal paper before and after heating respectively; f is a schematic diagram of the structural color thermal paper for thermal printing; g-h and i-j are respectively the digital photos and the reflection spectrum signals of the structural color thermal sensitive paper before and after printing.
In FIG. 2, a and b-g are digital photographs of printed patterns of structural color thermal paper prepared from PEG with different molecular weights, and reflection spectrograms of the patterns and the background, respectively.
In FIG. 3, a is SiO with different sizes 2 And hollow SiO 2 TEM image of colloidal particles; b is an SEM image of photonic crystals formed by assembling the colloidal particles; c is a digital photo printed with simple patterns on the corresponding thermal paper; d. e is solid SiO 2 Reflection spectrum and color gamut coordinates of the background and pattern parts on the thermal paper; f. g is hollow SiO 2 The reflection spectrum and color gamut coordinate of the background and pattern parts on the thermal paper.
In fig. 4, a and b are optical micrographs, designs and comparisons of actual sizes and resolutions respectively after different size dot matrixes are printed on the photonic crystal thermal sensitive paper; d, e are optical micrographs, designs and actual size and resolution comparison of the photonic crystal thermal sensitive paper printed with linear arrays of different widths respectively; c. f is high-resolution pattern and bar code photo printed on the thermal paper.
FIG. 5 a is a drawing showing different gray levels designed on a computer; b. c are respectively hollow SiO 2 And solid SiO 2 Printing results of corresponding gray scales on the photonic crystal thermal sensitive paper; e. d, g and f are respectively hollow SiO 2 And solid SiO 2 Patterns on the photonic crystal thermal sensitive paper and reflection spectra adopting different gray scales are adopted.
In fig. 6, a is a digital photo of patterns on the photonic crystal thermal sensitive paper and the ordinary thermal sensitive paper under different strong light irradiation times; b. c is the color difference change between the pattern and the background and the color difference change between the pattern or the background part and the initial state of the pattern or the background part on the two kinds of paper along with the prolonging of the irradiation time; d is a digital photo of patterns on the photonic crystal thermal sensitive paper and the common thermal sensitive paper at different heating temperatures; e. f is the color difference change between the pattern and the background and the color difference change between the pattern or the background part and the normal temperature (25 ℃) state of the pattern or the background part on the two kinds of paper respectively along with the rise of the heating temperature.
FIG. 7 shows the actual printing effect and reflection spectrum of the thermal sensitive paper prepared by combining the polyethylene glycol phase change layer and the solid photonic crystal layer with different thicknesses.
In fig. 8, a-c are digital photographs of thermosensitive paper prepared from silica-polyethylene glycol, silica-octadecanol and silica-paraffin, respectively, after the thermosensitive paper is used for thermosensitive printing.
In FIG. 9, a-d are digital photographs of thermosensitive paper for thermosensitive writing, which are prepared by using polystyrene colloidal particles, silica colloidal particles, hollow phenolic resin colloidal particles and hollow silica colloidal particles as assembly elements, respectively.
In fig. 10, a-d are respectively the photonic crystal thermal sensitive paper prepared by using ethanol, propanol, butanol and propylene carbonate as solvents and the digital photos obtained by thermal printing.
In fig. 11, a-d are digital photographs of a thermosensitive coating and thermosensitive printed characters thereof prepared on four substrates of paper, a polyvinyl chloride film, glass and an epoxy resin film, respectively.
In FIG. 12, a-c are digital photographs and reflection spectra of thermal sensitive paper made on transparent polyester film before and after printing; d-f is the pattern and the reflection spectrum of the photonic crystal thermal sensitive paper prepared on the white paper before and after printing.
In FIG. 13, a-b are digital photographs and reflection spectra of patterns printed by 90-degree hot stamp on PEG-10000 structural color thermal sensitive paper; c-d is a digital photo and a reflection spectrum of characters written on the PEG-10000 structural color thermal sensitive paper by a 180-degree heating pen.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1. Preparation of structural color thermal sensitive paper of thermochromic photonic crystals, comprising the steps of:
(1) Preparation of SiO 2 Film(s)
Taking 80 mu L of SiO with the size of 235nm 2 The colloidal particles were ultrasonically dispersed in 140. Mu.L of ethylene glycol solution to prepare a colloidal solution, 60. Mu.L of the colloidal solution was dropped on a black PET substrate, and the colloidal solution was uniformly spread to form a liquid film having a thickness of about 25 μm by a knife coating method. Standing at room temperature until a large number of crystal grains are discharged, transferring the photonic crystal liquid film to a 90 ℃ oven, and completely volatilizing the solvent to obtain the solid photonic crystal film.
(2) Preparation of PEG film
And (2) placing the solid PEG-4000 in a 90 ℃ oven to heat and melt, then dropwise adding 100 mu L of melted PEG solution on the transparent PET film, spreading PEG into a liquid film with the thickness of 10 mu m by adopting a blade coating method, and obtaining the solid PEG film with the thickness of 10 mu m after re-solidification.
(3) Laminating to form photonic crystal structure color thermal sensitive paper
SiO prepared by the steps (1) and (2) 2 The film is opposite to the front side of the PEG film, and the structural color thermal sensitive paper of the thermochromic photonic crystal can be obtained by using an adhesive material to adhere along the edges of the two films.
Example 2 color changing principle of structural color thermal sensitive paper of thermochromic photonic crystal
As shown in fig. 1a to e, in the structural color thermal sensitive paper of the thermochromic photonic crystal having a dual-layer structure prepared in example 1 of the present invention, the PEG layer undergoes a thermal phase change from a solid state to a liquid state and enters the inter-colloidal-particle pores of the photonic crystal layer instead of air under a heating condition, so as to induce an increase in the total refractive index and realize a color change.
Example 3 printing two-dimensional code on structural color thermal paper of thermochromic photonic crystals
As shown in FIGS. 1f-j, before printing, the structural color thermal paper of the thermochromic photonic crystal prepared in example 1 of the present invention exhibited a uniform green color because the PEG layer was optically transparent in the two-layer structure and the thermal paper exhibited SiO completely 2 The color of the photonic crystal. The digital terminal is placed in a commercial thermal printer, and the precise heating of a thermal printing head is controlled through a program, so that a two-dimensional code pattern on the digital terminal is printed on thermal paper. The reflection spectrum shows that the reflection wavelength of the pattern part is red-shifted by about 60nm compared with that of the background part; the thermally printed pattern can be clearly identified by the color change.
Example 4 Effect of PEG molecular weight on thermal printing Effect
The realization of the color change on the structural color thermosensitive paper of the thermochromic photonic crystal is based on the refractive index change caused by the thermal phase change of PEG. The thermal printing results are therefore directly related to the molecular weight and phase transition temperature of PEG. As can be seen from fig. 2, when the molecular weight of PEG is less than 1500, the phase transition temperature is low, and the structural color thermal sensitive paper of the thermochromic photonic crystal prepared according to embodiment 1 of the present invention is prone to phase transition at room temperature, so that the printed pattern is difficult to identify; when the molecular weight of PEG is 1500-6000, the structural color of the pattern of the thermochromic photonic crystal prepared in embodiment 1 of the invention after printing is obviously different from that of the background, so that the pattern can be successfully printed; when the molecular weight of PEG is greater than 10000, the temperature of the print head is not high enough to cause phase change, and thus a pattern cannot be printed.
Example 5 color composition and control of patterned background on Photonic Crystal Structure color thermal sensitive paper
The color of the structural color thermosensitive paper of the thermochromic photonic crystal can be adjusted by changing the size of the colloidal particles. As shown in FIG. 3, siO with a thickness of 199nm,235nm and 256nm 2 The colloidal particles are assembly elements, and blue, green and orange structural color paper can be obtained. The same is carried out on hollow SiO with the sizes of 253nm,262nm and 286nm respectively 2 The colloidal particles are assembly units, and blue, cyan and green photonic crystal paper can be obtained. The films are respectively compounded with PEG films to obtain the structural color thermal sensitive paper of the thermochromic photonic crystals with different colors. The six thermochromic photonic crystal structural color thermal sensitive papers are printed in a thermal sensitive mode, and patterns and backgrounds with different color combinations can be obtained. The corresponding reflection spectrum and color gamut coordinate measurement show that the solid SiO 2 Compared with the background part, the refractive index ratio of the medium of the pattern on the photonic crystal thermal sensitive paper is reduced, the color saturation of the pattern area is reduced, and the color is dark; in contrast, hollow SiO 2 On the photonic crystal thermal sensitive paper, the refractive index contrast of the pattern area and the background part is further increased, the color saturation of the pattern is increased, and the color is brighter.
Example 6 implementation of high-resolution printing on Photonic Crystal thermal paper
As shown in fig. 4, the dot matrix and line pattern of 4 different sizes were first designed to have diameters and line widths of 252 μm,168 μm,84 μm and 42 μm, respectively. The dot matrix and the line pattern were printed on the structural color thermal paper of the thermochromic photonic crystal prepared in example 1 of the present invention. The results show that the actual sizes of the dots and lines on the structural color thermal paper of the thermochromic photonic crystal prepared according to example 1 of the present invention are very close to those of the structural color thermal paper when the design sizes are 252 μm,168 μm and 84 μm, and the corresponding dot resolutions are 91dpi,149dpi and 298dpi and the line resolutions 127lpi,267lpi and 267lpi respectively. When the design size is 42 μm, the actual sizes of the dots and lines on the structural color thermal sensitive paper of the thermochromic photonic crystal prepared in example 1 of the invention are 84 μm and 93 μm respectively, which are higher than the design values, and the corresponding dot resolution and line resolution are 298DPI and 267LPI. This is because the highest resolution of the commercial thermal printer is 300DPI, and is limited by the minimum size of the printer thermal head capable of programming independent response, and cannot print finer information, so the resolution of the pattern on the structural color thermal paper of the thermochromic photonic crystal prepared in example 1 of the present invention cannot be further improved. The floral pattern and barcode pattern in fig. 4 demonstrate that the above-described resolution is sufficient to enable printing of various fine patterns.
Example 7 implementation of Gray-Scale printing Effect on Photonic Crystal Structure color thermal paper
In the experiment, the invention realizes the effect of different gray levels by regulating and controlling the spatial pixel density of the structural color. As shown in FIG. 5, in green hollow SiO 2 On the thermal paper, the number of red pixel points generated by printing is gradually increased along with the increase of the gray level until the paper is completely red. In the corresponding reflection spectrum, the intensity of the reflection peak at 564nm gradually decreases with the increase of the pixel point concentration, and the reflection peak at 633nm appears and the intensity gradually increases. On green solid SiO 2 On the structural color thermal sensitive paper, the concentration of dark red pixel points obtained by thermal printing is gradually increased along with the increase of the gray level until the whole paper is completely changed into dark red. In the corresponding reflection spectrum, the intensity of the reflection peak at 531nm gradually decreases until disappears, and simultaneously the reflection peak at 594nm appears and the intensity gradually increases. The lotus and mountain hills patterns in FIG. 5 demonstrate that the pixel spatial density control mechanism can achieve six-gray-scale pattern printing.
Example 8 comparison of photostability of Photonic Crystal Structure color thermal paper with that of Normal thermal paper
The structural color thermal sensitive paper of the thermochromic photonic crystal prepared by the embodiment of the invention does not contain any dye, and the color is only related to a physical structure, so that the structural color thermal sensitive paper has good illumination stability. In the experiment, a high-light-intensity xenon lamp is adopted to simulate sunlight to irradiate a sample, and the illumination fading process in the daily use environment is accelerated to show.
As shown in fig. 6a-c, when two kinds of paper (the left side of fig. 6a is the normal thermal paper, and the right side is the photonic crystal structure color thermal paper) were irradiated under the xenon lamp for 4 hours at the same time, the pattern on the structural color thermal paper of the thermochromic photonic crystal prepared according to the embodiment of the present invention did not change, but the pattern on the normal thermal paper gradually faded. With the increase of the irradiation time, the color difference between the pattern on the common thermal paper and the background is gradually reduced, and the pattern disappears; the color difference between the pattern on the structural color thermal sensitive paper of the thermochromic photonic crystal prepared by the embodiment of the invention and the background is almost kept unchanged, so that the pattern can still be displayed. By comparing the color difference of the same pattern or background area before irradiation and after different irradiation times, the fading of the common thermal sensitive paper can be found to be mainly due to the reversible change of the dye at the pattern; the pattern of the structural color thermal sensitive paper of the thermochromic photonic crystal prepared by the embodiment of the invention is not faded mainly because the structural color has better stability to irradiation.
Example 9 comparison of thermal stability of Photonic Crystal Structure color thermal paper with that of Normal thermal paper
The thermal stability of the structural color thermal sensitive paper of the thermochromic photonic crystal prepared by the embodiment of the invention is related to the PEG phase transition temperature, the thermal stability of the common thermal sensitive paper is related to the chemical reaction of the coloring layer, and the two have similar thermal stability. In an experiment, the structural color thermal sensitive paper of the thermochromic photonic crystal prepared in the embodiment of the invention and common thermal sensitive paper are heated at different temperatures, and the stability of the structural color thermal sensitive paper and the common thermal sensitive paper under the real condition is simulated and displayed.
As shown in fig. 6d-f, when the temperature is less than 60 ℃, the patterns are still clearly visible when both papers (the left side of fig. 6d is the common thermal paper and the right side is the photonic crystal structure color thermal paper) are kept unchanged. When the temperature is higher than 60 ℃, the background part of the structural color thermal sensitive paper of the thermochromic photonic crystal prepared by the embodiment of the invention is changed from green to red, the color difference between the pattern and the background is sharply reduced, and the pattern cannot be displayed; in the conventional thermal paper, only the background portion is changed from white to gray, the color difference between the pattern and the background is slightly reduced, and the pattern is still visible. When the temperature further rises to 90 ℃, the background of the common thermal paper becomes black, the color difference between the pattern and the background is gradually reduced, and the pattern disappears. By comparing the color difference of the same pattern or background area before heating and at different heating temperatures, the color change of the common thermal sensitive paper is mainly found to be caused by the fact that the dye at the background generates a chemical color reaction during heating; the color change of the structural color thermal sensitive paper of the thermochromic photonic crystal prepared by the embodiment of the invention is caused by that the PEG in the background area is subjected to physical phase change when being heated, and the PEG is changed into a liquid state from a solid state and permeates into pores among colloidal particles to cause the increase of the refractive index.
EXAMPLE 10 actual printing Effect on structural color thermal paper combining different thickness thermal phase Change layer and solid Photonic Crystal layer
As shown in fig. 7, when the thickness of the PEG phase change layer was 3 μm and the thickness of the solid photonic crystal layer was gradually increased from 5 μm to 10 μm, the pattern after thermal printing was clearly visible with a wavelength change of about 60 nm. When the thickness of the solid photonic crystal layer was further increased to 12 μm and 15 μm, the color change of the pattern region after thermal printing was insignificant compared to the background portion, and at the same time, the corresponding reflection spectrum position did not change, and pattern printing failed. This is because, when the ratio of the PEG layer thickness to the thickness of the solid photonic crystal layer is too small, the melted PEG is insufficient to completely fill the amount of PEG required for the inter-colloidal pores in the solid photonic crystal layer, the pores are partially filled, and thus the photonic crystal layer does not change color significantly. Therefore, in the thermochromic photonic crystal structure color thermal paper, the ratio of the thickness of the PEG layer to the thickness of the solid photonic crystal layer is more than 0.3.
EXAMPLE 11 structural color thermal paper made of different phase Change materials and Effect of thermal printing thereof
As shown in FIG. 8, when the thermal phase change layer is made of polyethylene glycol, stearyl alcohol, and paraffin, respectively, the thermal phase change layer is made of silicon dioxide (SiO) 2 The solid photonic crystal layer is compounded to obtain the photonic crystal structure color thermal sensitive paper, and clear patterns can be obtained by printing on three kinds of paper by adopting the same thermal printing mode, which shows that the preparation method of the thermal sensitive paper is suitable for various phase change material systems.
EXAMPLE 12 Photonic Crystal Structure color thermal paper made of different Assembly elements and thermal printing Effect thereof
As shown in fig. 9, when the solid photonic crystal layer in the thermal paper has assembly elements of polystyrene colloidal particles, silica colloidal particles, hollow phenolic resin colloidal particles and hollow silica colloidal particles, which are respectively compounded with the phase-change thin layer, the corresponding structural color thermal paper can present a uniform structural color. And when the structural color thermal sensitive paper is subjected to thermal sensitive printing by using a heating pen direct writing mode, obvious color change can occur in a heating area and clear printing handwriting can be presented, so that the preparation method of the structural color thermal sensitive paper is suitable for various colloidal particle systems.
Example 13 structural color thermal paper made with different solvents and thermal printing Effect thereof
As shown in fig. 10, taking silica gel particles as an example, ethanol, propanol, butanol, and propylene carbonate as dispersing solvents can be ultrasonically dispersed to obtain colloidal solutions in different solvents. The colloidal solution is coated on the substrate by adopting a blade coating method, and the four colloidal solutions can be converted to obtain a uniform structural color film. The obtained solid photonic crystal layer is respectively compounded with the thermal phase change material layer to obtain the structural color thermal sensitive paper, and clear patterns and obvious color change can be presented after thermal sensitive printing. Therefore, the preparation of the photonic crystal structure color thermal sensitive paper is suitable for various solvents.
EXAMPLE 14 structural color thermosensitive layers prepared on different substrates and thermally printed letters thereof
As shown in fig. 11, the double-layer structure thermal sensitive paper can be constructed on paper, polyvinyl chloride film, glass substrate, phenolic resin film by preparing solid photonic crystal film on different base materials in advance and then compounding with thermal phase change material layer, thereby realizing the preparation of structural color thermal sensitive paper on different base materials. The writing of the character information can be realized on the thermal paper by utilizing a thermal printing mode of direct writing by a heating pen. Therefore, the photonic crystal thermosensitive material can be constructed on different substrates.
EXAMPLE 15 structural color thermal paper made on white or transparent substrate and thermal printing Effect thereof
As shown in fig. 12, besides the black base, the invention only needs to add a small amount of nano carbon black in the colloidal solution, and the structural color thermal paper can be prepared on the transparent base material or the white paper (fig. 12a-b are transparent base materials, fig. 12c-d are white paper). After the two kinds of thermal paper are respectively subjected to regionalization thermal printing, clear patterns can be presented. The double-layer structure color thermal sensitive paper prepared by the embodiment of the invention is suitable for base materials with different colors.
Example 16 printing of characters and designs on PEG-10000 structural color thermal paper
As shown in fig. 13, as the molecular weight of PEG increases further, its melting point increases and the heat provided by the existing thermal printing apparatus does not enable printing. This problem can be solved by providing more heat with higher temperature heating devices, such as: the printing of patterns or the writing of characters can be successfully realized on the paper by adopting a 90-degree hot stamping stamp or a 180-degree heating pen, and in the corresponding reflection spectrum, the wavelength difference of about 60nm is generated between the background and the patterns, which indicates that the color is obviously changed after the writing or the printing, and the hot printing on the high-molecular-weight structural color thermal sensitive paper is realized.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (9)

1. The structural color thermal sensitive paper based on the thermochromic photonic crystals is characterized by comprising a thermal phase change material layer and a solid photonic crystal layer; the solid photonic crystal layer contains colloidal particles; under the heating condition of the thermal sensitive paper, the thermal phase change material layer is melted and permeates into gaps among colloidal particles of the solid photonic crystal layer, the refractive index of the solid photonic crystal layer is increased, and color change is generated; the thermal sensitive paper is stable in color development, and the color cannot fade with illumination.
2. The photonic crystal structural color thermal paper according to claim 1, wherein the thermal phase change material is coated on the lower surface of the transparent protective layer to form a thermal phase change material layer; the transparent protective layer is selected from one or more of a polypropylene film, a nylon film, a polyester film, a polyvinyl chloride film and a polyethylene film; the thermal phase change material is selected from polyethylene glycol, polyvinyl alcohol, paraffin, ethylene-vinyl acetate copolymer, heneicosane, forty-alkyl, octadecanol and eicosanol.
3. The photonic crystal structured color thermal paper according to claim 1, wherein the solid photonic crystal is coated on the upper surface of the base material to form a solid photonic crystal layer; the base material is selected from one or more of black, white or transparent polypropylene film, nylon film, polyester film, polyvinyl chloride film, polyethylene film, coated paper, paperboard, glass and epoxy resin film; the colloidal particles are selected from one or more of polystyrene, silicon dioxide, hollow silicon dioxide, zinc sulfide, zinc oxide, titanium dioxide, cerium oxide, ferroferric oxide, polymethyl methacrylate, tin oxide, copper oxide and hollow phenolic resin with uniform size; the size of the colloidal particles is 100-400nm.
4. A preparation method of structural color thermal sensitive paper based on thermochromic photonic crystals is characterized by comprising the following steps:
(1) Coating the supersaturated solution containing the colloidal particles on a substrate, and heating to volatilize the solvent to obtain a solid photonic crystal film;
(2) Heating the thermal phase-change material to be molten at the temperature higher than the phase-change temperature, uniformly coating the thermal phase-change material on the transparent protective layer, and re-solidifying to obtain a thermal phase-change film;
(3) And (3) enabling the front surfaces of the solid photonic crystal film and the thermal phase change film to be opposite, and attaching the two layers of films along the edges by using a viscous material to obtain the photonic crystal structure color thermal sensitive paper.
5. The method according to claim 4, wherein in the step (1), the supersaturated solution containing colloidal particles is a colloidal particle dispersion comprising 20 to 50% by volume of colloidal particles and 50 to 80% by volume of a solvent; the base material is one or more of a black, white or transparent polypropylene film, a nylon film, a polyester film, a polyvinyl chloride film, a polyethylene film, coated paper, paperboard, glass and an epoxy resin film; the colloidal particles are one or more of polystyrene, silicon dioxide, hollow silicon dioxide, zinc sulfide, zinc oxide, titanium dioxide, cerium oxide, ferroferric oxide, polymethyl methacrylate, tin oxide, copper oxide and hollow phenolic resin with uniform size; the solvent is selected from one or more of water, glycol, ethanol, dimethyl sulfoxide, dimethylformamide, propylene carbonate, methanol, propanol and butanol.
6. The method according to claim 4, wherein in the step (2), the protective layer is one or more of a transparent polypropylene film, a nylon film, a polyvinyl chloride film, a polyester film or a polyethylene film; the thermal phase change material is one or more of polyethylene glycol, polyvinyl alcohol, paraffin, ethylene-vinyl acetate copolymer, heneicosane, forty-alkyl, octadecanol and eicosanol.
7. The method according to claim 4, wherein in the step (3), the adhesive material is various kinds of glue or double-sided tape.
8. Structural color thermal paper based on thermochromic photonic crystals prepared by a method according to any of claims 4 to 7.
9. Use of the thermochromic photonic crystal-based structural color thermal paper according to claim 1 or 8 for high resolution pattern printing, gray scale pattern printing and heated straight-writing thermal paper in commercial thermal printers.
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