Systems and methods for producing and using photonic crystal printing ink solutions - Patents.com

Abstract

A novel system and method for the generation and use of photonic crystal printing ink solutions is provided. Systems and methods for use in or in association with the generation and printing of photonic crystal forming ink solutions that use block copolymers and, optionally, solvents. The color of the printed ink solution can be set by a single or multiple block copolymer mixture (i.e., premix coloring) or by printing multiple layers of individual single or multiple block copolymer mixtures (i.e., post-print coloring). One or more compositions used by the systems and methods function as structural color (i.e., photonic crystal) precursors. Formulating, dosing, printing, and optional post-printing treatment of the ink solution on a substrate functions to provide a desired photonic crystal printed object with reflective colored properties.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 149,943, filed February 16, 2021, which is incorporated herein by reference in its entirety.

[0002]

[0002] The present invention relates generally to the field of photonic crystal formation, and more specifically to novel and useful systems and methods for generating and printing photonic crystal-forming ink solutions. [Background technology]

[0003]

[0003] Color formation, and in particular the creation of new colors for use, is a field that has been under development for thousands of years. Although research and development continues, the technology for forming and then applying / printing color has been primarily focused on the development of new colors through the development of dyes and pigments.

[0004]

[0004] Dyes are organic compounds that are usually extracted from plants or produced synthetically (e.g. indigo or alizarin). Dyes provide useful colorants that may or may not be toxic, but they are limited in variety. Furthermore, printing / applying dyes to a substrate (e.g. clothing) may require strong organic solvents that may be toxic. Pigments are dry coloring substances, usually insoluble particles mixed with a solvent, typically derived from coal tar and petrochemicals. Pigments offer a much wider variety of colors than dyes, but can be very toxic.

[0005]

[0005] Thus, dyes and pigments have many limitations. For example, dyes and pigments are limited by the need to discover and create new chemicals to produce new colors. For example, to use red and blue dyes or pigments separately, two different molecules must be synthesized. Many dyes and pigments are potentially toxic, so their production and / or use can be dangerous. Materials colored with dyes or pigments tend to fade over time as the dyes or pigments slowly disperse and / or decompose over time (e.g., the chromophores that generate the color can decompose). Furthermore, effect pigments (also called interference pigments) contain relatively large particles, limiting their use in printing, especially in inkjet printing.

[0006]

[0006] Structural color, and in particular some synthetic photonic crystals, offer an alternative to dyes and pigments for imparting value-added optical effects to objects. The reflective coloring imparted by photonic crystals is due to the physical geometry of the material, rather than to absorption bands as with traditional dyes. Thus, synthetic photonic crystals offer the potential to decouple the color produced by a material from chemical functional groups, avoiding the need for toxic and unstable chromophores. Summary of the Invention

[0007]

[0007] Thus, there is a need in the art of color formation, reflective material formation, and printing for more consistent color formation and printing methods that are non-toxic, are not limited by the creation or discovery of new chromophores, have unique optical properties, and do not fade over time. The present invention provides such a new and useful system and method. [Brief description of the drawings]

[0008] [Figure 1]

[0008] FIG. 1 is a diagram of a typically implemented color gamut. [Diagram 2]

[0009] FIG. 1 is a diagram of benchmark inkjet ink solutions. [Diagram 3]

[0010] FIG. 1 is a diagram of a non-optimal inkjet ink solution. [Figure 4]

[0011] 1 is an image of suboptimal droplet formation. [Diagram 5]

[0012] 1 is an ink solution formulation for an exemplary system. [Figure 6]

[0013] FIG. 2 is a diagram of the viscoelastic properties of the ink solution of an exemplary system. [Figure 7]

[0014] 1 is a formulation of an ink solution for an exemplary system containing a co-binder. [Figure 8]

[0015] FIG. 2 is a diagram of the viscoelastic properties of the ink solution of an exemplary system. [Figure 9]

[0016] 1 is an image of good drop formation of an ink solution in an exemplary system. [Figure 10]

[0017] 1 is an image of good drop formation of an ink solution of an exemplary system. [Figure 11]

[0018] 1 is an image of a photonic crystal printout. [Figure 12]

[0019] 1 is a formulation of an ink solution for an exemplary system for forming a structurally colored printed object. [Figure 13]

[0020] 1 is an exemplary radical curing screen printing solution formulation for forming structurally colored objects. [Figure 14]

[0021] 1 is an exemplary cationic curing screen printing solution formulation for forming structurally colored objects. [Figure 15]

[0022] 13 is an optical measurement of a structurally colored object in some included exemplary systems. [Figure 16]

[0022] Optical measurements of structurally colored objects in some included exemplary systems. [Figure 17]

[0023] FIG. 1 is a schematic diagram of a printing system. [Figure 18]

[0024] 1 is a flow chart of a method for printing with a photonic crystal forming ink solution. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009]

[0025] The following description of the embodiments of the invention is intended to enable those skilled in the art to make and use the invention, but not to limit the invention to those embodiments.

[0010] 1. Overview

[0026] Systems and methods for or associated with the generation and printing of photonic crystal forming ink solutions may include the use of block polymer mixtures and solvents. The color of the printed ink solution can be set by a single or multiple block polymer mixture (i.e., premixed coloring) or by printing multiple layers of individual single or multiple block polymer mixtures (i.e., post print coloring). One or more compositions used by the systems and methods function as structural color (i.e., photonic crystal) precursors. The formulation, loading, printing, and optional post-printing treatment of the ink solution on a substrate function to provide a desired photonic crystal printed object with reflective properties.

[0011]

[0027] The system and method can be used in any field or application requiring reflective inks and coatings. In fields requiring high-end coloring, such as cosmetics, printing, sporting goods, packaging, security marketing, and automotive, the system and method may be particularly useful. The system and method may be implemented for any coloring and / or printing application. The system and method are particularly suited for inkjet printing in general, and more specifically, industrial inkjet printing. The system and method may also be implemented for other types of printing, including, but not limited to, screen printing, thermal printing, flexographic printing, and rotogravure printing.

[0012]

[0028] The systems and methods may offer many potential advantages: Colors produced by photonic crystal forming inks may be significantly less toxic than currently used pigments and dyes.

[0013]

[0029] Furthermore, objects coated with photonic crystal-forming inks may be more compatible with current recycling processes.

[0014]

[0030] Furthermore, objects using photonic crystal forming inks can have unique optical properties.

[0015]

[0031] The systems and methods may also provide the advantage of a simple formulation workflow for generating multiple different colors from a few material inputs.

[0016]

[0032] Additionally, photonic crystal forming inks may provide a more "resilient" form of printing that is less prone to fading than traditional pigments and dyes.

[0017]

[0033] In inkjet printing, the systems and methods may enable printing of higher molecular weight, or "larger," polymer molecules than currently used, i.e., the brush block copolymers may provide low solution viscosity and shear thinning properties that enable inkjet printing of "larger" polymers.

[0018]

[0034] The systems and methods may provide a cheaper method of printing reflective materials compared to current technology. Through the use of a co-binder, the systems and methods can provide significantly larger volumes of printable ink solution at a lower cost compared to current products.

[0019]

[0035] The systems and methods may provide a way to print UV reflective coatings ranging from, but not limited to, 200-400 nm wavelengths.

[0020]

[0036] The systems and methods may provide a way to print visible light reflective coatings ranging from, but not limited to, 400-750 nm wavelengths.

[0021]

[0037] The systems and methods may provide a way to print infrared reflective coatings ranging from, but not limited to, 750-2000 nm wavelengths.

[0022]

[0038] The systems and methods may provide a way to print new or expanded color gamuts compared to current technology. By using additive color mixing, the systems and methods may provide colors that are generally not achievable using currently available pigments and colorants and through the application of subtractive color theory.

[0023]

[0039] Additionally, the systems and methods can be improved when used with pigments and dyes. The systems and methods can combine photonic crystal forming inks with pigments and dyes to enable a wide range of colors, including unique colors, by mixing subtractive and additive color theories to generate a color gamut.

[0024]

[0040] The systems and methods can provide a number of potential advantages. The systems and methods are not limited to providing such advantages in any particular case, but are presented only as exemplary representations of how the systems and methods can be used. The list of advantages is not intended to be exhaustive, and other advantages may exist in addition or alternatively.

[0025] 2. Composition for the Ink Solution (System 1)

[0041] The composition for a printable photonic crystal forming ink solution includes at least one block copolymer 110 and at least one solvent 120. Once deposited on a substrate, the composition functions as a non-particulate print solution that forms reflective structures (i.e., structural color). That is, the composition functions as a block copolymer-based solution that is optimized and / or enhanced for printing. Once "printed," the composition is deposited as a "film" on the printing surface with an appropriately specified surface area, thickness, color, and design, as determined by the printing method and desired implementation.

[0026]

[0042] In a preferred variation, the photonic crystal structure has a relatively periodic microstructure within the deposited film, with an average periodicity appropriate for the desired color wavelength (or desired color waveband). The system can vary widely depending on the embodiment (e.g., for the type of printing method implemented, the printer implemented, the target substrate, and the desired output). Depending on the embodiment, the solution can also include co-solvents, co-binders, and expansion agents, as well as paint, ink, or coating additives. Coating additives include, but are not limited to, surfactants, humectants, crosslinkers, photoinitiators, photosensitizers, leveling agents, adhesion promoters, rheology modifiers, plasticizers, stabilizers, and any number of other additives.

[0027]

[0043] As used herein, substrate refers to any surface to which the composition can be applied.Depending on the embodiment and the ink solution composition, the substrate that can be used may vary widely.Examples of substrates that can be used may include packaging materials, sporting goods, automotive surfaces, credit cards, watch faces, footwear, paper, organic fabrics, synthetic fabrics, plastics, metals, walls, etc.

[0028]

[0044] As a "coloring" property of the ink solution, the ink solution composition allows different color ink solutions to be combined to produce different mixture colors. The ink solutions may allow both additive coloring (e.g., RGB coloring in a monitor) and subtractive coloring (e.g., CYMK coloring in a printer). As part of additive coloring, different color ink solutions can be mixed to produce a new color film that corresponds to the average wavelength of the photonic crystal forming ink solutions. This mixing can be performed before printing the composition onto the substrate, or as part of the printing process where the ink solutions are mixed during or after deposition onto the substrate. As part of subtractive coloring, different ink solutions can be layered together with pigments or dyes so that each ink solution film layer absorbs the desired color spectrum to leave the desired color.

[0029]

[0045] Color mixing can also be performed by depositing different ink solutions on a substrate and curing or drying between each deposition. In this way, given a standard color base (e.g. RGB coloring), colors other than the basic color can be obtained by sequentially depositing constituent layers of blue, green, or red.

[0030]

[0046] In some variations, the ink compositions may be useful for pointillistic "coloring," i.e., small dots of various colors can be deposited such that the human eye cannot distinguish one from the other without magnification.

[0031]

[0047] The color value is measured by L *a * b color space. * a * b color space or L * a * The Lb color model (i.e., the CIELAB color model) is known to those skilled in the art. * a * The b color model is standardized, for example, in DIN EN ISO / CIE11664-4:2020-03. * a * Each perceivable color in the b color space is represented by a coordinate in the three-dimensional coordinate system {L * ,a * ,b}. * The axis describes the green or red portion of the color, with negative values ​​representing green and positive values ​​representing red. * The axis describes the blue or yellow portion of the color, with negative values ​​representing blue and positive values ​​representing yellow. Thus, the lower the number, the more bluish the color. * The axis is perpendicular to this plane and represents lightness. * C * h color model is L * a * Similar to the b-color model, but using cylindrical coordinates instead of Cartesian. * C * In the h-color model, L * represents lightness, and C represents lightness. * represents the saturation and h represents the hue angle. * The value of is the lightness axis (L * ) from the surface of the sample. These values ​​are measured using a Konica Minolta CM5 spectrophotometer. Analysis of the samples is performed according to the Konica Minolta CM5 standard operating procedures.

[0032]

[0048] As used herein, references to color, printed color, or design refer to ink solutions that form photonic crystals (structural color) when applied to a substrate and dried. Nanostructured or microstructured materials (e.g., by a self-assembly process) reflect the desired printed color and / or design. For example, when referring to a green ink solution, this refers to an ink solution that leaves photonic crystals that reflect green light when dried. Depending on the embodiment, the "purity" or saturation of the green color can also be manipulated. That is, depending on the embodiment, a green ink solution can refer to an ink solution that leaves photonic crystals that reflect only green light when dried (i.e., a narrow light reflection waveband centered around the wavelength range observed as green) or an ink solution that reflects primarily green (i.e., a broad band of light is reflected with a peak reflection centered around green). Depending on the embodiment, the structural color ink solution can be dried to leave photonic crystal structures with a desired reflection spectrum.

[0033]

[0049] The system allows the construction of reflective photonic crystal structures capable of reflecting extremely narrow or broad wavelength bands. Thus, as used herein, wavelength (or reflected wavelength) generally refers to a wavelength band in the electromagnetic spectrum, as with printed color. Unless otherwise specified, the use of the term wavelength (or color) does not in any way limit the invention to wavelengths within the visible spectrum and / or to narrow or broad wavelength bands.

[0034]

[0050] In one variation, a composition for a printable photonic crystal forming ink solution may include at least one block polymer and at least one solvent.

[0035]

[0051] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one swelling polymer.

[0036]

[0052] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder.

[0037]

[0053] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, at least one swelling polymer, and at least one co-binder.

[0038]

[0054] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, wherein the at least one solvent includes a reactive monomer or oligomer.

[0039]

[0055] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, wherein the at least one solvent includes water.

[0040]

[0056] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, wherein the at least one co-binder includes a crosslinking functional group.

[0041]

[0057] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, the co-binder including sucrose acetate isobutyrate (SAIB-100).

[0042]

[0058] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, the co-binder including a cellulose ester resin.

[0043]

[0059] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, the co-binder including sucrose benzoate.

[0044]

[0060] In another variation, a composition for a printable photonic crystal forming ink solution can include at least one block polymer, at least one solvent, a swelling agent, and at least one co-binder, the at least one co-binder including a cross-linking molecule.

[0045]

[0061] In another variation, the composition for the printable photonic crystal forming ink solution may include at least one block polymer, at least one solvent, and at least one co-binder. The at least one co-binder includes a cross-linking molecule. The composition may further include a swelling agent. The swelling agent contains a cross-linking functional group.

[0046]

[0062] In another variation, the composition for a printable photonic crystal-forming ink solution can include at least one block polymer, at least one solvent, and at least one co-binder, where the at least one co-binder includes a cross-linking molecule. This variation further includes a combined dry state prior to the addition of the at least one solvent, which can become a functional printable photonic crystal-forming ink solution upon the addition of the at least one solvent.

[0047]

[0063] In another variation, the composition for the printable photonic crystal forming ink solution may include at least one block polymer, at least one solvent, and at least one co-binder. The viscosity of the ink is adjusted to 1-20 cP at 25° C. for inkjet printing applicability.

[0048]

[0064] In another variation, the viscosity of the ink is adjusted to 1,000 cP to 10,000 cP at 25° C. for screen printing applicability.

[0049]

[0065] In another variation, the composition for the printable photonic crystal forming ink solution may include at least one block polymer, at least one solvent, and at least one co-binder. The viscosity of the ink is adjusted to 10 cP to 300 cP at 25° C. for flexographic and gravure printing applications.

[0050]

[0066] In these variations, and all variations, changing the temperature changes the viscosity.

[0051]

[0067] The system may include at least one block copolymer 110. The block copolymer 110 serves as a scaffold for forming ordered nano- or microstructures from which color emerges. That is, the block copolymer 110 allows the ink solution to self-assemble into photonic crystals or structural colors. Each block copolymer 110 includes molecules with an arrangement of blocks (e.g., linear, brush, star) linked via reactive ends. Each block copolymer 110 can form different ordered phases at nanoscale to fine scale lengths. Each block copolymer can correspond to a specific color, and / or at least one block copolymer can correspond to an ink solution containing multiple block copolymers that together correspond to one color.

[0052]

[0068] The brush block copolymers and the corresponding constituents of the brush block copolymers can be prepared by the general methods described in WO2020 / 180427 and US2021 / 0395463 A1. Additionally or alternatively, other methods may be employed to prepare the brush block copolymers.

[0053]

[0069] Depending on the embodiment, the at least one block copolymer 110 comprises up to 80% by weight of the ink solution. In one embodiment, the block copolymer 110 comprises approximately 1-10% of the ink solution. In another embodiment, the block copolymer 110 comprises 10%-20% of the ink solution. In another embodiment, the block copolymer 110 comprises 20%-30% of the ink solution. In another embodiment, the block copolymer 110 comprises 30%-40% of the ink solution. In another embodiment, the block copolymer comprises approximately 40%-50% of the ink solution. In another embodiment, the block copolymer 110 comprises 50%-60% of the ink solution. In another embodiment, the block copolymer 110 comprises 60%-70% of the ink solution. In another embodiment, the block copolymer comprises 70%-80% of the ink solution. In another embodiment, the block copolymer 110 comprises 80%-90% of the ink solution.

[0054]

[0070] The at least one block copolymer 110 may include any type of block copolymer depending on the need or desire of the embodiment. Examples of types of block copolymer 110 include brush block copolymer, wedge type block copolymer, hybrid wedge copolymer, linear block copolymer, or any other type of block copolymer. Depending on the embodiment, all block copolymers may be of a single type or of various types. For example, in one embodiment, the at least one block copolymer 110 may include two brush block copolymers. In another example, the at least one block copolymer 110 may include two brush block copolymers and one wedge type block copolymer. In a third example, the at least one block copolymer 110 includes a single block copolymer that includes both a brush block and a linear block.

[0055]

[0071] In some variations, the at least one block copolymer 110 comprises a brush block copolymer (also known as a block polymer having a bottle-brush polymer architecture, or a graft copolymer). In some examples, the brush block copolymer may have a tailored graft density (e.g., by copolymerization of polymeric macromonomers and reactive diluents). Additionally or alternatively, the at least one block copolymer may comprise multiple brush block copolymers. The brush block copolymer may provide shear thinning properties; that is, the lack of entanglement of the polymer chains of the brush block copolymer may result in a solution that is less viscous than a "typical" solution of a polymer of similar size and / or molecular weight but that does not have a brush architecture.

[0056]

[0072] Brush block copolymers with various graft densities can be prepared by the general method described in US2021 / 0395463A1, Supporting Information by T.-P. Lin et al., JACS 2017, 139(10), pp. 3896-3903, and Supporting Information by T.-P. Lin et al., ACS Nano, 2017, 11(11), pp. 11632-11641.

[0057]

[0073] In some brush block copolymer variants, the block copolymer 110 can utilize highly tunable brush block copolymers. These brush block copolymers can have two or more polymer blocks, at least one of which has one or more preselected properties. For example, in an embodiment of a graft copolymer comprising two polymer blocks (a first polymer block and a second polymer block), the first polymer block can have a preselected graft density, a preselected graft distribution, and / or a preselected degree of polymerization. The second polymer block may or may not have a preselected graft density, a graft distribution, and / or a degree of polymerization. The second polymer block can be the same or different depending on the needs of the embodiment (which may also be the case for additional polymer blocks of the graft copolymer in a more general embodiment). In this way, the block copolymer can have a highly tunable and deterministic nature. This in turn can contribute to the high tunability and versatility of the self-assembled structures and related methods of the present invention.

[0058]

[0074] In any embodiment of the brush block copolymer, the brush block copolymer may have a preselected graft density. The preselected graft density may be any value selected from the range of 0.01 to 1.00 (unitless specific density). In other words, the amount (concentration) of the diluent and macromonomer and their components may be preselected to obtain a preselected graft density that is any value within the range of 0.01 to 1.00. That is, in any embodiment of the method of synthesizing a graft copolymer disclosed herein, the graft density may be selected from the range of 0.01 to 1.00. For example, depending on the embodiment, the graft density may be selected from the range of 0.01 to 0.32, 0.32 to 0.34, 0.34 to 0.49, 0.49 to 0.51, 0.51 to 0.65, 0.65 to 0.68, 0.68 to 0.75, or 0.75 to 1.00.

[0059]

[0075] In variations in which at least one block copolymer comprises multiple brush block copolymers, the first brush block copolymer may have a preselected first graft density (also referred to above as graft density). Thus, additional brush block copolymers, i.e., second block copolymer, third brush block copolymer, ..., Nth block copolymer, may have corresponding preselected graft densities, i.e., second graft density, third graft density, ..., Nth graft density. As previously mentioned, graft density may also vary within each block copolymer, with distinct blocks of distinct block copolymers having distinct properties (e.g., distinct graft densities). In any embodiment of the brush graft copolymer methods disclosed herein, any graft density (i.e., first graft density through Nth graft density) may be selected within the range of 0.01 to 1.00. In any embodiment of the method of synthesizing a graft copolymer disclosed herein, any graft density (i.e., the first graft density through the Nth graft density) may be selected from the range of 0.01 to 1.00. In any embodiment of the method of synthesizing a brush graft copolymer disclosed herein, any graft density (i.e., the first graft density through the Nth graft density) may be selected from the range of 0.01 to 0.32, 0.32 to 0.34, 0.34 to 0.49, 0.49 to 0.51, 0.51 to 0.65, 0.65 to 0.68, 0.68 to 0.75, or 0.75 to 1.00.

[0060]

[0076] Polymer molecular weight: Number average molecular weight (M n ) and weight average molecular weight (M W); and molecular weight distribution: polydispersity index (PDI) can be determined by gel permeation chromatography (GPC) using a combination of differential refractive index (dRI) and two light scattering (LS) detectors. The use of an LS detector allows the analysis of the absolute molecular weight of the polymer samples. The solvent used for all samples was tetrahydrofuran (THF) and the elution rate was 1.0 mL / min. The polymer samples were completely dissolved in HPLC grade THF at concentrations ranging from 2.5 to 7.5 mg / mL, passed through a 0.5 μm syringe filter, and injected by an autosampler. The porous column stationary phase consisted of two Malvern T600 single-hole columns with an exclusion limit of 20,000,000 Da for poly(styrene). The molecular weight and PDI were determined by OMNISEC software.

[0061]

[0077] Generally, a brush block copolymer sample contains a molecular weight distribution quantified by PDI. Modifying the PDI can function to increase or decrease the intensity of one or more reflected wavelengths and / or lambda max (wavelength of strongest reflection) of a deposited coating containing the brush block copolymer. In many variations, the uniformity of the brush block copolymer can be controlled by the production conditions. In one variation of the brush block copolymer, the polydispersity index of the graft copolymer can be selected from the range of 1.00 to 1.30. In another variation, the polydispersity index of the graft copolymer can be selected from the range of 1.00 to 1.20. In another variation, the polydispersity index of the graft copolymer can be selected from the range of 1.00 to 1.10.

[0062]

[0078] In some variations, each block copolymer of at least one block copolymer 110 may include one or more molecular structures that organize into a photonic crystal. Depending on the embodiment, the block copolymer 110 may provide a scaffolding for such structures that, once dried, form a desired color composition (i.e., form a photonic crystal that reflects one or more desired wavelengths of light). In one variation, the block copolymer 110 includes a single block molecular structure, and the single block solution forms a photonic crystal having a specific reflection wavelength. Alternatively, the block copolymer 110 includes multiple blocks, and the multiple block solution forms a photonic crystal having a specific reflection wavelength corresponding to each block. In some variations, the composition exhibits a photonic band gap (wavelength of maximum reflection) at a wavelength within a range of about 200 nm to about 2000 nm.

[0063]

[0079] In other variations, the composition may exhibit a photonic band gap with a wavelength within the range of about 200 nm to 400 nm, 400 nm to 750 nm, 750 nm to 1600 nm, or any combination of two or more of these ranges. In other variations, the at least one block copolymer 110 includes two or more block copolymers. For example, the at least one block copolymer 110 includes a mixture of two block copolymers, a first block copolymer and a second block copolymer, and the mixture solution of the block copolymers forms a photonic crystal of a particular color by the mixture solution. With two or more block copolymers 110, a spectrum of colors can be generated by varying the relative concentration of the first block copolymer to the concentration of the second block copolymer. That is, an ink solution composed only of the first block copolymer 110 can provide a first color, and an ink solution composed only of the second block copolymer can provide a second color. An ink solution containing various ratios of the first block copolymer 110 and the second block copolymer can have any color from the color spectrum between the first color and the second color, depending on the ratio of the number of first block copolymers to the number of second block copolymers.

[0064]

[0080] In some variations, the at least one block copolymer 110 may include three or more block copolymers. As with two block copolymers, the relative ratio of each block copolymer can determine the color and other properties of the ink solution. Mixtures of multiple block copolymers 110 can be used to generate any range of colors with different reflectances, chromaticities, opacities, and brightness.

[0065]

[0081] In one variant, the system may include a plurality of photonic crystal-forming ink solutions. Each ink solution includes at least one block copolymer 110. In this variant, each ink solution (based on a corresponding block copolymer mixture) may correspond to a specific color. Thus, different colors can be generated by additive coloring mixing or overlaying (e.g., by printing different ink solutions of different concentrations on top of each other). For example, the system may include a first ink solution corresponding to a first color (e.g., red), a second ink solution corresponding to a second color (e.g., green), and a third ink solution corresponding to a third color (e.g., blue). By layering three ink solutions of different concentrations, a RGB gamut of colors can be obtained, as shown in FIG. 1. Similarly, any general additive color gamut can be obtained.

[0066]

[0082] The ink solution may include a solvent 120. The solvent functions to help maintain the solubility of the other ink solution components. In many variations, the system may further include multiple solvents 120, i.e., co-solvents. The solvent / co-solvents may further impart desired properties to the ink solution. Depending on the embodiment, a wide variety of solvents may be used to provide the desired properties required for the embodiment. For example, the solvent 120 may allow modification of the coating properties of the solution, provide a slow or fast drying range to suit the printer, optimize inkjet printing / jetting, help modify the ink solution viscosity, and / or modify the ink solution drying rate on the print media. Depending on the embodiment, the solvent 120 itself may be a reactive component. That is, in some variations, the solvent 120 may include a reactive component, such as an acrylate or methacrylate monomer or oligomer, or an epoxy monomer or oligomer, or any combination thereof. In one variation, the solvent 120 includes a reactive monomer or oligomer. Alternatively, the solvent may include other reactive components. The reactive component solvent 120 may be necessary when using a UV curable ink composition. The solvent 120 may comprise water or any suitable organic solvent common to those skilled in the art and may be used as an organic solvent or co-solvent in the ink solution formulation. The term "organic solvent" is known to those skilled in the art, in particular from Council Directive 1999 / 13 / EC (11 March 1999).Examples of such organic solvents include heterocyclic, aliphatic or aromatic hydrocarbons or partially fluorinated variants thereof, such as 4-chlorobenzotrifluoride, mono- or polyhydric alcohols, in particular methanol and / or ethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, benzyl alcohol, butyl lactate, ethers, esters, such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, ketones, such as acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, toluene, xylene, butanol, ethyl glycol and butyl glycol and their acetates, ethyl glycol and butyl glycol and their acetate ethers, butyl diglycol, diethylene glycol dimethyl ether, or mixtures thereof.

[0067]

[0083] In some variations, the system includes at least one swelling agent. The at least one swelling agent may comprise up to 70% of the ink composition. The at least one swelling agent may function to adjust the solution viscosity (e.g., adjust the viscosity by 2 to 4 orders of magnitude) and / or to modify the color of the coating. In some variations, the swelling agent may include a linear polymer. Examples of linear polymeric expanding agents are optionally substituted aliphatic polyesters, poly(amino acids), copoly(ether-esters), polyalkylene oxalates, polyamides, poly(iminocarbonates), polyorthoesters, polyoxaesters, polyamide esters, polyoxaesters containing amino groups, poly(anhydrides), polyphosphazenes, polysiloxanes, polyethylene, polyethylene terephthalate, poly(tetrafluoroethylene), polycarbonates, polypropylene, polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), poly(lactide-co-glycolide) (PLGA), polydioxanone (PDO), trimethylene carbonate (TMC), and the like. Examples of suitable polymeric materials include polyvinyl carbonate, polyethylene glycol (PEG), polyurethane, polyacrylonitrile, polyaniline, polyvinylcarbazole, polyvinyl chloride, polyvinyl fluoride, polyvinylimidazole, polyvinyl alcohol, polystyrene and poly(vinylphenol), aliphatic polyesters, polyacrylates, polymethacrylates, polystyrene, chlorosulfonated polyolefins, and copolymers thereof. Additionally or alternatively, block or non-linear polymer architectures as described above may be used as the expanding agent (e.g., star, dendritic, cyclic).

[0068]

[0084] In some variations, the swelling agent may include the above polymers that have been modified to allow for self-crosslinking or crosslinking with other molecules or compounds.

[0069]

[0085] In some variations, the system may include at least one co-binder component (also referred to as an excipient). The co-binder may provide a number of functions. The functions of the co-binder may include reducing solution viscosity, increasing solution viscosity, improving mechanical properties of the ink solution as a coating, improving coating durability, reducing the glass transition temperature of the coating, increasing the glass transition temperature of the coating, improving coating performance in the presence of temperature cycling, providing water resistance of the coating, providing humidity resistance of the coating, improving ink solution wetting on the substrate, improving coating adhesion on the substrate, improving optical properties of the coating by increasing saturation, improving optical properties of the coating by reducing haze. Generally speaking, the co-binder may include any non-volatile material that is not a brush block copolymer or an expanding polymer. The co-binder may be reactive or non-reactive. In variations where reactive co-binders are implemented, the co-binder may provide cross-linking, adhesion, or other "binding" properties. Depending on the embodiment, the co-binder may constitute a portion or a majority of the composition. The co-binder may include resins comprised of polystyrenes, polyesters, polyolefins, polyvinyl ethers, polyethers, polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polyurethanes, polysiloxanes, polyamides, polyethylene terephthalates, polybutylene terephthalates, polyvinyl chlorides, melamine resins, phenolic resins, urea resins, alkyd resins, epoxy resins, polyether ketones, polyphenylene sulfides, polyvinyl alcohols, and / or copolymers thereof, and / or acrylate / methacrylate functionalized variants thereof, and / or epoxy functionalized variants thereof. The co-binder may include a cellulose ester resin or a sucrose ester compound. The co-binder 140 may comprise up to 70% of the solution. In some variations, the co-binder may include a cellulose acetate butyrate resin. In some variations, the co-binder includes sucrose acetate isobutyrate (SAIB-100). In some variations, the co-binder includes sucrose benzoate.

[0070]

[0086] In some variations, the ink solution may include one or more stabilizers. The stabilizers function to improve the stability of the ink solution, i.e., to improve the life span of the solution and / or the solubility of the solution. The stabilizers may also function to improve the stability of the coating. Examples of types of stabilizers include UV absorbers (e.g., benzotriazoles), hindered amine light stabilizers (HALS), antioxidants, and thiosynergists. In some variations, crosslinking functional groups may be incorporated. Depending on the variation, crosslinking functional groups may be incorporated with co-binders and / or expansion agents. In some variations, suitable crosslinking functional groups may include one or more olefinic double bonds. They may be high molecular weight (oligomeric) or low molecular weight (monomeric). Examples of monomers with one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or 2-hydroxyethyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, or ethyl methacrylate. Examples of monomers with two or more double bonds are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, or bisphenol A diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, or tetraacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, or tris(2-acryloylethyl)isocyanurate. Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, polyurethanes, polyethers, and polyesters which are acrylated or contain vinyl ether or epoxy groups.Another example of an unsaturated oligomer is an unsaturated polyester resin prepared primarily from maleic acid, phthalic acid, and one or more diols, and having a molecular weight of about 500 Da to 3,000 Da. In some variations, a suitable crosslinking functional group may include one or more epoxy units. The component is preferably an alicyclic epoxy compound and / or may be a glycidyl ether compound. The alicyclic epoxy compound may be a cycloalkane oxide-containing compound obtained by epoxidizing a cycloalkane-containing compound with an oxidizing agent. The cycloalkane of the cycloalkane oxide-containing compound may be cyclohexene or cyclopentene. The glycidyl ether compound may be a diglycidyl or polyglycidyl ether obtained by reacting an aliphatic polyhydric alcohol or its alkylene oxide adduct with epichlorohydrin. Examples of polyhydric alcohols include alkylene glycols, such as ethylene glycol, propylene glycol, and 1,6-hexanediol. In some variations, a suitable crosslinking functional group may include an oxetane or polyol. In some variations, suitable crosslinking functional groups may include one or more vinyl ether compounds. Examples include divinyl or trivinyl ether compounds, such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether.

[0071]

[0087] The ink solution may include one or more photoinitiators. For the photopolymerization of ethylenically unsaturated compounds, phosphine oxides are well-known photoinitiators. Commercially available examples of phosphine oxides include IRGACURE 819 (BASF SE) and DAROCUR TPO (BASF SE). Alpha-hydroxyketone compounds are also photoinitiators that may be used. Commercially available examples of alpha-hydroxyketone compounds include ESACURE KIP 150 (DKSH Management, ltd), IRGACURE 127 (BASF SE), IRGACURE 2959 (BASF SE), and IRGACURE 184 (BASF SE).

[0072]

[0088] The ink solution may also include a photosensitizer suitably configured to absorb radiation from the light source and facilitate energy transfer to the photoinitiator. The photosensitizer may include an anthracene, pyrene, carbazole, thiazine, phenothiazine, or thioxanthene moiety.

[0073]

[0089] In some variations, the composition may further include a substrate. The printable photonic crystal ink solution is applied to the substrate. That is, the composition may include a printable photonic crystal ink solution including at least one block copolymer, at least one solvent, and at least one co-binder, and a substrate. The printable photonic crystal ink solution forms a structural color film on the substrate. Depending on the embodiment, the printable photonic crystal ink solution may include additional co-solvents, swelling agents, and paint, ink, and coating additives, as described above. The substrate may include any suitable surface or porous material, and application of the printable photonic crystal ink solution allows for the formation of a colored film surface on the substrate or (for porous materials) within the substrate. Depending on the embodiment, the substrate may include organic or inorganic materials. Examples of substrates include skin, organic tissue, organic fibers, synthetic fibers, wood, metal, cement, plastic, stone, plaster, walls, and membranes.

[0074]

[0090] As mentioned above, the system may have many variations of ink composition. Herein, several exemplary ink composition systems for inkjet printing are presented. In addition to the above-mentioned ink solution components, certain rheological conditions must also be achieved for good inkjet printing. As shown in the benchmark ink solution example in FIG. 2, as the vibration frequency increases, the viscosity is preferably uniform or decreases (black curve), and the elastic and viscous coefficients increase with frequency. The elastic coefficient is always lower than the viscous coefficient (red curve). In comparison, in the alternative poor rheology of inkjet printing shown in FIG. 3, the elastic coefficient dominates the viscous coefficient at high printing frequencies. In addition, for a good ink solution, suitable inkjet conditions (e.g. temperature and inkjet frequency) are also required. As illustrated in FIG. 4, several failed inkjet drop formation attempts are shown.

[0075]

[0091] In a first variation of the inkjet ink solution, as shown in Figure 5, the solution comprises at least one block copolymer, at least one swelling agent, and a solvent. The at least one swelling agent comprises polylactic acid (PLA) and polystyrene (PS), and the solvent comprises 4-chlorobenzotrifluoride. The at least one block copolymer may be any block copolymer and / or combination of block copolymers (e.g., a combination of block copolymers that are printed in a desired color).

[0076]

[0092] In one example (A1), the concentration of the at least one block copolymer is about 5%-10%, the concentration of PLA is about 1.0%-7.5%, the concentration of PS is about 1.0%-7.5%, and 4-chlorobenzotrifluoride comprises about 82%-92% of the solution.

[0077]

[0093] In a second example (A2), the concentration of the at least one block copolymer is about 5%-10%, the concentration of PLA is about 2.5%-7.5%, the concentration of PS is about 2.5%-7.5%, and 4-chlorobenzotrifluoride constitutes about 79.5%-89.5% of the solution.

[0078]

[0094] In a third example (A3), the concentration of the at least one block copolymer is about 5%-10%, the concentration of PLA is about 2.5%-7.5%, the concentration of PS is about 2.5%-7.5%, and 4-chlorobenzotrifluoride constitutes about 79%-89% of the solution.

[0079]

[0095] In a fourth example (A4), the concentration of the at least one block copolymer is about 5%-10%, the concentration of PLA is about 1.0%-7.5%, the concentration of PS is about 1.0%-7.5%, and 4-chlorobenzotrifluoride constitutes about 80%-90% of the solution.

[0080]

[0096] As shown in Figure 6, these four examples of the first variant (i.e., A1, A2, A3, and A4) satisfy the criteria that the viscosity is uniform or decreases and the elastic and viscous moduli increase as a function of frequency. Moreover, the viscous moduli are always greater than the elastic moduli.

[0081]

[0097] In a second variation of the inkjet ink solution, as shown in Figure 7, the solution comprises at least one block copolymer, at least one swelling agent, at least one co-binder, and a solvent. The at least one swelling agent comprises polylactic acid (PLA) and polystyrene (PS), the at least one co-binder comprises SAIB-100, and the solvent comprises 4-chlorobenzotrifluoride. The at least one block copolymer may be any block copolymer and / or combination of block copolymers (e.g., a combination of brush block copolymers printed in a desired color).

[0082]

[0098] In one example of the second variation (B1), the concentration of the at least one block copolymer is about 5%-10%, the concentration of PLA is about 2.5%-7.5%, the concentration of PS is about 2.5%-7.5%, SAIB-100 is about 1%-5%, and 4-chlorobenzotrifluoride constitutes about 75%-85% of the solution.

[0083]

[0099] In a second example (B2) of the second variant, the solution further comprises a butyl acetate co-solvent. In the second example, the concentration of the at least one block copolymer is about 2.5%-7.5%, the concentration of PLA is about 1%-5%, the concentration of PS is about 1%-5%, the SAIB-100 is about 1%-5%, the butyl acetate co-solvent is about 35%-45% of the solution, and the 4-chlorobenzotrifluoride solvent is about 45%-55% of the solution.

[0084]

[0100] In a third example (B4) of the second variant, the solution further comprises an ethylene glycol diacetate co-solvent in addition to the butyl acetate co-solvent and the 4-chlorobenzotrifluoride solvent. In the third example, the concentration of the at least one block copolymer is about 2.5%-7.5%, the concentration of PLA is about 1%-5%, the concentration of PS is about 1%-5%, the SAIB-100 is about 1%-5%, the butyl acetate co-solvent is about 10%-20% of the solution, the EDGA co-solvent is about 15%-25% of the solution, and the 4-chlorobenzotrifluoride solvent is about 45%-55% of the solution.

[0085]

[0101] In a fourth example (D3) of the second variant, the concentration of the at least one block copolymer is about 2.5%-7.5%, the concentration of PLA is about 1%-5%, the concentration of PS is about 1%-5%, SAIB-100 is about 1%-5%, the butyl acetate co-solvent is about 2.1%-12.5% ​​of the solution, the EDGA co-solvent is about 30.7%-40.7% of the solution, and the 4-chlorobenzotrifluoride solvent is about 42.5%-52.5% of the solution.

[0086]

[0102] As shown in Figure 8, in a third example of the second variant, B4 meets the criteria for good inkjet. As shown in Figure 9, good jetting can be achieved with B4 ink solution, jetting is performed at 25C printing with 2kHz jetting frequency. As shown in Figure 10, in a fourth example of the second variant, good jetting can be achieved with D3 ink solution, jetting is performed at a driving voltage of 22V and a drop velocity of 4.1m / s. Figure 11 shows a sample print with D3 ink with suitable print parameters.

[0087]

[0103] In a third variation of the inkjet ink solution, as shown in Figure 12, the solution comprises at least one block copolymer, at least one swelling agent, at least one co-binder, and at least one solvent, where the at least one swelling agent comprises polylactic acid (PLA) and polystyrene (PS), the at least one co-binder comprises SAIB-100 or sucrose benzoate, and the at least one solvent comprises ethyl 3-ethoxypropionate and ethylene glycol diacetate.

[0088]

[0104] In one example (E1) of the third variation, the concentration of the at least one block copolymer (BBCP4) is about 2.5%-7.5%, the concentration of PLA is about 1%-4%, the concentration of PS is about 1%-4%, the SAIB-100 is about 1%-4%, the ethyl 3-ethoxypropionate co-solvent is about 60%-85% of the solution, and the ethylene glycol diacetate co-solvent is about 5%-10% of the solution.

[0089]

[0105] In a second example (E2) of the third variant, the concentration of the at least one block copolymer (BBCP5) is about 2.5%-7.5%, the concentration of PLA is about 1%-4%, the concentration of PS is about 1%-4%, the SAIB-100 is about 1%-4%, the ethyl 3-ethoxypropionate co-solvent is about 60%-85% of the solution, and the ethylene glycol diacetate co-solvent is about 5%-10% of the solution.

[0090]

[0106] In a third example (E3) of the third variant, the concentration of the at least one block copolymer (BBCP4) is about 2.5%-7.5%, the concentration of PLA is about 1%-4%, the concentration of PS is about 1%-4%, the sucrose benzoate is about 1%-4%, the ethyl 3-ethoxypropionate co-solvent is about 60%-85% of the solution, and the ethylene glycol diacetate co-solvent is about 5%-10% of the solution.

[0091]

[0107] In a fourth example (E4) of the third variant, the concentration of the at least one block copolymer (BBCP6) is about 2.5%-7.5%, the concentration of PLA is about 1%-4%, the concentration of PS is about 1%-4%, the sucrose benzoate is about 1%-4%, the ethyl 3-ethoxypropionate co-solvent is about 60%-85% of the solution, and the ethylene glycol diacetate co-solvent is about 5%-10% of the solution.

[0092]

[0108] In a variant (F1) of the radical curing screen printing solution, as shown in Figure 13, the solution comprises at least one block copolymer, at least one reactive co-binder, at least one reactive solvent, and at least one photoinitiator, where the at least one block copolymer comprises BBCP5, the reactive solvent comprises tetrahydrofurfuryl acrylate, the reactive co-binder comprises aliphatic triacrylate oligomer Sartomer CN133, and the photoinitiator is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

[0093]

[0109] In a variation (G1) of the cationic curing screen printing solution, as shown in Figure 14, the solution comprises at least one block copolymer, at least one solvent, at least one reactive co-binder, at least one additive, at least one photoinitiator, and at least one photosensitizer, where the at least one block copolymer is BBCP5, the solvent is butyl acetate, the at least one reactive co-binder is the difunctional cycloaliphatic epoxide Lambson UviCure S105, the at least one additive is the monofunctional oxetane Lambson UviCure S140, the at least one photoinitiator is the cationic photoinitiator Lambson SpeedCure 938 of the iodonium hexafluorophosphate family, and the at least one photosensitizer is a thioxanthone Lambson SpeedCure CPTX.

[0094]

[0110] As mentioned above, the at least one block copolymer included in the ink solution is specific to the examples and can be varied as desired. Several sample brush block copolymers are presented herein and can be used individually, together, or as part of a separate mixture of at least one block copolymer. The number average molecular weight (Mn) of the exemplary brush block copolymers can be in the range of 400 kDa to 4,000 kDa, more preferably in the range of 500 kDa to 3,000 kDa, and even more preferably in the range of 600 kDa to 2,500 kDa. A first example brush block copolymer (BBCP1) can have an Mn of 1,072 kDa, a weight average molecular weight (Mw) of 1,890 kDa, and a polydispersity index (PDI) of 1.126. A second example brush block copolymer (BBCP2) can have a number average molecular weight (Mn) of 799.4 kDa, a weight average molecular weight (Mw) of 850.9 kDa, and a polydispersity index (PDI) of 1.064. A third example brush block copolymer (BBCP3) can have a number average molecular weight (Mn) of 1,072 kDa, a weight average molecular weight (Mw) of 1,180 kDa, and a polydispersity index (PDI) of 1.101. A fourth example brush block copolymer (BBCP4) can have a number average molecular weight (Mn) of 541.0 kDa, a weight average molecular weight (Mw) of 585.1 kDa, and a polydispersity index (PDI) of 1.082. A fifth example brush block copolymer (BBCP5) can have a number average molecular weight (Mn) of 2,088 kDa, a weight average molecular weight (Mw) of 2,236 kDa, and a polydispersity index (PDI) of 1.071. A sixth example brush block copolymer (BBCP6) can have a number average molecular weight (Mn) of 1,287 kDa, a weight average molecular weight (Mw) of 1,396 kDa, and a polydispersity index (PDI) of 1.085. Formulations containing BBCP preferably form reflective coatings in the wavelength range of 200 nm to 1600 nm. Depending on the needs of each example, these sample brush block copolymers can be incorporated as part of the exemplary ink solutions described above.The sample brush block copolymers may be incorporated into the ink solution as a single brush block copolymer or as a mixture of two or more brush block copolymers, with the ratio of these brush block copolymers setting the color of the ink solution. Sample examples of these embodiments are provided in Figures 5, 6, 12, 13, and 14. For example, in an embodiment of A1, at least one block copolymer includes BBCP1. In an example of an embodiment of A2, at least one block copolymer includes BBCP1. In an example of an embodiment of A3, at least one block copolymer includes BBCP2. In an example of an embodiment of A4, at least one block copolymer includes a desired ratio of BBCP1 and BBCP2.

[0095]

[0111] In one embodiment of B1, at least one block copolymer comprises BBCP3. In one embodiment of B2, at least one block copolymer comprises BBCP3. In one embodiment of B4, at least one block copolymer comprises BBCP3. In one embodiment of D3, at least one block copolymer comprises BBCP3. In one embodiment of E1, at least one block copolymer comprises BBCP4. In one embodiment of E2, at least one block copolymer comprises BBCP5. In one embodiment of E4, at least one block copolymer comprises BBCP6. Optical samples of each formulation are provided in FIG. 15. Each sample was generated using inkjet printing with 60 passes and 1 kHz frequency in binary print mode.

[0096]

[0112] In one embodiment of F1, at least one block copolymer includes BBCP5. In one embodiment of G1, at least one block copolymer also includes BBCP5. Optical samples of each formulation are provided in Figure 16. Each sample was produced using screen printing.

[0097] 3. Printing System

[0113] As shown in Fig. 17, a printing system for structural ink includes an ink container system 210 including at least a first ink container, each ink container containing a structural ink solution, the first ink container containing a first structural color solution, the first structural color solution including a first distinct block copolymer or a first distinct block copolymer mixture, a deposition system 220 capable of producing a photonic crystal deposit by depositing a printing solution onto a substrate, and a dosing mechanism 230 connected to the ink container system and the deposition system, which, once a print order is received, builds the printing solution by dosing an appropriate amount of the appropriate structural color solution into the deposition mechanism. The system functions to enable structural color printing, i.e., the system stores, prepares, and prints structural color designs onto a substrate.

[0098]

[0114] The printing system can incorporate or use any structural color printable ink solution, or any combination of structural color printable ink solution and another type of color solution (e.g., pigment or dye), but may be particularly applicable for use with the ink compositions described herein. Furthermore, the system can be part of any currently available printing system and / or printing method, where the printing system provides the components for using structural inks for printing. Although this document focuses on this printing system incorporating inkjet printing, the system can generally be used with any suitable system and method for printing. Examples of other printing techniques / systems that can be combined with this system include inkjet printing, offset printing, flexography, screen printing, rotogravure printing, etc.

[0099]

[0115] In some variations of the printing system, the included printer components are inkjet printer components. Examples of included printer components are an inkjet well, an inkjet printhead, a premixed fluid system, and / or a heating element.

[0100]

[0116] As used herein, substrate refers to any object, material, and / or surface suitable for receiving the printing solution. Once the printing solution is "printed" onto the substrate, it dries into a film containing the periodic photonic crystal structure. Depending on the type of printing, the desired substrate, and the desired implementation, the system components may include versatility to enhance printing on the substrate. The appropriate substrate may depend on the particular structural color solution formulation. Examples of substrates that can be used include paper, metal, wood, fabric (organic or synthetic), stone, plastic, and biological (e.g., human skin).

[0101]

[0117] The system may include an ink container system 210. The ink container system 110 functions to store the structural color solution and keep the solution easily accessible for use. The ink container system 210 includes at least a first ink container (also called a well), which stores a first structural color solution.

[0102]

[0118] In embodiments where only single color printing is performed, a single ink container system may be appropriate. In variations where multicolor printing is used, two ink containers may be used. The system may have any number of ink containers, with each ink container containing a separate structural color solution. That is, in general, an N-container system may include additional ink solutions such that a first ink container contains a first structural color solution, a second ink container contains a second structural color solution, and an Nth ink container contains an Nth structural color solution.

[0103]

[0119] For example, in a two-container system, a first container can contain a first structural color solution (e.g., red) and a second container can contain a second structural color solution (e.g., blue). In an example of a three-container system, a first container can contain a first structural color solution (e.g., red), a second container can contain a second structural color solution (e.g., green), and a third container can contain a third structural color solution (e.g., blue). In an example of a four-container system, a first container can contain a first structural color solution (e.g., red), a second container can contain a second structural color solution (e.g., green), a third container can contain a third structural color solution (e.g., blue), and a fourth container can contain a fourth non-structural color solution (e.g., a black dye or pigment).

[0104]

[0120] In some inkjet embodiments, the reservoir system 210 may include an inkjet well, in which case the ink reservoir is an inkjet well. The inkjet well may serve to store an ink solution. In some variations, the inkjet well may include a multi-well, i.e., a well having multiple storage chambers. Each well of the multi-well may store a separate ink solution. The separate ink solutions may be mixed to obtain various color solutions. It is also possible for the multi-well to allow mixing of the separate ink solutions. In variations where ink solutions are used as part of a premixed printer embodiment, the printer components may include a fluidic system or other suitable ink mixing mechanism such that the printer components may mix separate ink solutions of different concentrations to generate a color spectrum prior to printing (e.g., prior to ejecting the mixed ink from the inkjet printer head). In post-printing mixing embodiments (e.g., additive or hybrid additive / subtractive coloring embodiments where multiple layers of separate ink solution colors are layered on top of each other), the multi-well may allow storage and eventual dispersion (e.g., by the inkjet printer head) of the ink solution.

[0105]

[0121] The container system may also include components or features that aid in maintaining and stabilizing the structural color solution. Examples of components that may be included as part of the container system or within each ink container include heating elements (e.g., for heated storage to improve viscosity) and mixing elements (e.g., to prevent separation, settling, etc. of the structural color solution).

[0106]

[0122] The system can include a deposition system 220. The deposition system 220 functions to "print" the printing solution onto the substrate. Depending on the embodiment, the deposition system 220 can set the printing speed, thickness, and design as the printing solution is deposited onto the substrate.

[0107]

[0123] Depending on the embodiment, the deposition system 220 can print the entire design (projection, color, etc.) onto the substrate in one pass, or the deposition system can make multiple "passes" over the substrate, with each pass being a different color pass containing a different color.

[0108]

[0124] In some inkjet variations, the deposition system 220 may include an inkjet printer head. The inkjet printer head may function to enable the dispersion of an ink solution onto a substrate. The inkjet printer head may be of any desired type. Examples of inkjet printer heads include MEMS printer heads, piezoelectric printer heads, thermal inkjet printer heads, continuous inkjet printer heads, and / or any other desired type of printer head. As part of the ink solution distribution, the inkjet printer head may enable a particular inkjet firing frequency, ink solution droplet size, and nozzle density. In some variations, the inkjet printer head may also have an adjustable drive voltage (e.g., a MEMS printer head). The deposition system allows the ink characteristics to be changed by varying the printing frequency and printing waveform. In variations including a piezoelectric printer head, the waveform may be changed by varying the voltage.

[0109]

[0125] The system may include a dosing mechanism 230. The dosing mechanism may be connected to the ink container system 210 and the deposition system 220. The dosing mechanism functions to prepare a printing solution (for printing) from the structural color solution. In a single color embodiment, the dosing mechanism 230 may directly transfer a first structural color solution to the deposition system 220. In a multi-color embodiment, the dosing mechanism 230 may select the time and amount of each structural color to transfer to the deposition system 220. This may be particularly true for preprint coloring embodiments. In some variations, the dosing mechanism 230 may function in conjunction with the deposition system 220. That is, the dosing mechanism 230 may "dosage" the deposition system 220 continuously during the functioning of the printing system.

[0110]

[0126] In variants where the color is set before printing (i.e. preprint color), the dosing mechanism may include a mixing device. The mixing device serves to combine the different structural color solutions into a single printing solution. That is, for a desired printing color and a desired printing volume (and potentially other printing properties, e.g. viscosity), the dosing mechanism takes all the necessary structural color solutions in the correct ratio and places them in the mixing device, where they are sufficiently homogenized to become a single printing solution.

[0111]

[0127] In one example, the mixing device includes a mechanical mixer / stirrer. In another example, the mixing device includes a magnetic mixer. Examples of mixing methods that may be used by the mixing device include high shear mixing, sonication, centrifugation, and planetary mixing.

[0112]

[0128] In some variations, the mixing device can include a premixed fluid system. The premixed fluid system can include circuitry for controlling the mixing of the ink container elements prior to printing. In some variations, the premixed fluid system can further include an additional well / container for storing the mixed ink solution prior to printing.

[0113]

[0129] In some variations, the mixing device can generate pre-printed colors for later use. In these variations, the dosing mechanism 230 can obtain structural color ink solutions from the ink containers, generate new color structural color inks in the mixing device, and then send the new color structural color inks to the ink containers, which may or may not be empty. For example, the printing system may include a three-container system, where the first ink container contains a red structural color solution, the second ink container contains a blue structural color solution, and the third ink container is empty. In this variation, the dosing mechanism can obtain the red structural color solution and the blue structural color solution in the appropriate ratio to generate a green structural color solution, which is then sent into the third ink container. If the green structural color solution runs out during normal operation of the printing system, the dosing mechanism can generate additional green structural color solution to refill the third ink container, while the red and blue structural ink containers can be refilled externally.

[0114]

[0130] The dosing mechanism 230 can further enable the creation of a post-printing color design. In some variations, the printing system has a post-printing coloring mode, where the color design can be built on the substrate rather than before printing. In these variations, the dosing mechanism 230 can determine and deliver one structural color solution at a time to the deposition mechanism 220. Once the deposition mechanism 220 has printed one pass on the substrate, the dosing mechanism 230 can then deliver a different structural color solution to the deposition mechanism to enable the next printing pass on the substrate.

[0115]

[0131] Depending on the embodiment, the multi-pass post-printing color design may be additive or hybrid (i.e. additive / subtractive) coloring, and depending on this factor the system components may function differently. The dosing mechanism 230 may determine the "optimum" order of structural color solutions to achieve the desired printed brightness. Additionally, the deposition mechanism 220 may pause between passes to allow each printing pass to dry before adding the next printing pass. In additive coloring variants, the deposition mechanism 220 preferably does not include pauses to allow mixing of the structural color solutions on the substrate.

[0116]

[0132] In many variations, the printing system can include or be connected to a processor that allows for color calculations, i.e., the printing system can utilize processor functionality to determine the appropriate amounts of structural color solutions needed to produce a print and / or produce a particular color. This process can take into account the differences required for additive and subtractive coloring.

[0117]

[0133] In some variations, the printing system may include components for post-processing. In one example, the printing system includes a heating or UV curing element. The heating or UV curing element may function to heat the printing solution or initiate a reaction in the ink. This may be particularly useful for inkjet embodiments. The heating or UV curing element may function in conjunction with an inkjet printer head, where the heating element warms the inkjet solution for ink solution dispersion. The heating element may function to maintain beneficial solution properties for efficient jetting.

[0118] 4. Method

[0134] As shown in FIG. 18, a method for printing with a structural color ink solution includes obtaining an ink solution (S110), dosing the ink solution (S120), and printing a path with the ink solution (S130). Obtaining the ink solution may include setting an ink solution base color by adjusting the ink solution to appropriate printing conditions, setting an ink solution viscosity, and setting an ink solution drying time. Dosing the ink solution (S120) may include mixing the ink solution. Printing a path with the ink solution (S130) may include printing a desired design and performing a drying time delay. In some variations, the method may include printing multiple passes (e.g., of a print head) to deposit additional layers, or may include depositing additional layers using multiple print heads. In some variations, the method may include a post-processing step, i.e., post-processing the printing (S140). Post-processing the printing (S140) may be performed after each successive layer or after deposition of all layers.

[0119]

[0135] The method functions to print structural color designs onto a desired target object (i.e., substrate) using a block polymer photonic crystal forming ink solution. The method allows for multiple implementations of multi-color printing; that is, the method may allow for both premixed color implementations and / or color layering. Premixed colors include premixing the desired colors prior to printing the desired colors. Color layering may include printing multiple pass color layers to obtain the desired color. The method may preferably be implemented with the structural color ink solution system described above, but generally may be implemented for any photonic crystal forming ink based printing solution with target wavelengths outside the visible spectrum (ultraviolet and near infrared).

[0120]

[0136] By utilizing ink solutions based on structural colors, the method can provide additive and / or hybrid (additive / subtractive) coloring steps. One type of coloring method or a combination of coloring methods can be used to color the substrate. The method can be implemented together with previously generated coloring methods. For example, the method can use an existing subtractive coloring set (e.g., traditional CMYK inks) to allow for a variant of additive printing (e.g., using photonic crystal-forming inks). That is, the method can implement structural coloring in combination with pigment or dye coloring methods. The coloring method of the method can be implemented simultaneously with the pigment or dye coloring method (e.g., by premixing) or after (e.g., by layering the photonic crystal-forming ink solution above or below the pigment or dye coloring layer).

[0121]

[0137] The method may be applicable for use with any printing device capable of applying a solution to a substrate. The method may be particularly applicable to a printer (e.g., an inkjet printer). For example, in an inkjet printer embodiment, dosing the ink solution (S120) may further include heating the ink solution, but generally, the method may be used with any type of printing method, with minor variations in the implementation steps depending on the printing method. As part of the inkjet embodiment, the method may be implemented with both continuous inkjet (CIJ) with a printing frequency of up to 80-100 kHz, and drop-on-demand inkjet (DOD) with a printing frequency of up to 10-50 kHz and a drop velocity of up to 4-10 m / s. The method may be implemented with piezoelectric DOD, MEMS printing, and any other type of inkjet printing. Additionally, the method may be implemented in non-inkjet forms, such as screen printing, roto-screen printing, flexographic printing, rotogravure printing, and offset printing.

[0122]

[0138] As part of any printing embodiment, the method may be practiced with premixed color printing and / or post-printing color mixing. In premixed printing, the desired color of the print may be mixed before the solution is applied to the substrate, and the desired color may be directly printed in a single pass. In variations involving premixed color printing, depositing ink solutions (S120) may further include premixing the ink solutions into appropriate colors. In some variations of premixed color printing, obtaining ink solutions (S110) may include obtaining multiple ink solutions. Thus, depositing ink solutions (S120) may include mixing multiple ink solutions.

[0123]

[0139] In post-printing color mixing, the desired color can be achieved by mixing / layering colors on the substrate (i.e., achieving the desired color after printing). That is, a fixed set of colors is used to print the ink solution, and the desired color is achieved by multiple printing passes. Thus, the colors of the ink solution are layered until the desired color is achieved. Post-printing color mixing can include additive coloring (e.g., RGB), subtractive coloring (e.g., CMYK), or some hybrid combination of additive and subtractive coloring. In an embodiment of post-printing color mixing, printing a pass with the ink solution (S130) is called multiple times (i.e., printing multiple passes) to achieve the desired design, brightness, and color thickness / opacity with one or more desired colors. In additive post-printing color mixing, multiple photonic crystal forming inks can be mixed on the substrate to achieve the desired color. In hybrid additive / subtractive post-printing color mixing, multiple photonic crystal forming inks and pigment inks can be mixed on the substrate to achieve the desired color. Drying times exist between passes to allow the ink solutions to dry on top of each other to provide the desired hybrid additive / subtractive coloring.

[0124]

[0140] Depending on the type and color of the printing embodiment, acquiring the ink solution (S110) may include acquiring multiple ink solutions (e.g., different reflection wavelengths). Thus, acquiring the ink solution (S110) may further include setting the base color of the ink solution. Setting the base color of the ink solution may enable different types of coloring (e.g., additive and / or hybrid additive / subtractive printing) and serve to set the parameters of the printing embodiment. For example, in an additive printing embodiment, acquiring ink solutions of three base colors, namely red, blue, and green, may set the printing color gamut to be limited to the RGB gamut. Acquiring the ink solution (S110) may also include setting base ink solutions targeting reflection wavelengths outside the visible spectrum (e.g., ultraviolet or infrared).

[0125]

[0141] In a premixed example, obtaining the ink solution (S110) may include obtaining an ink solution that forms a photonic crystal that reflects a desired wavelength range. In an example for the full visible spectrum range, obtaining the ink solution (S110) may include obtaining an ink solution corresponding to a photonic crystal that reflects a wavelength of about 400 nm and a second ink solution corresponding to a photonic crystal that reflects a wavelength of about 750 nm. In an example for the ultraviolet spectrum range, obtaining the ink solution (S110) may include obtaining an ink solution corresponding to a photonic crystal that reflects a wavelength range of about 200 nm to 400 nm. In an example for the near ultraviolet range, obtaining the ink solution (S110) may include obtaining an ink solution corresponding to a photonic crystal that reflects a wavelength range of about 750 nm to 2000 nm.

[0126]

[0142] In some printer embodiments, obtaining the ink solution (S110) may include receiving at least one ink container at the printer system, which may correspond to filling or placing the ink container in the printer system. Depending on the printer system, the color, thickness, and general composition of the ink solution may depend on the embodiment.

[0127]

[0143] Block S120, which includes dosing ink solution, functions to prepare an ink solution and / or multiple ink solutions for printing. Dosing ink solution (S120) can vary depending on the printing embodiment. For example, in inkjet printing, dosing ink solution (S120) can include heating the ink solution. In premixed color embodiments, dosing ink solution (S120) can include mixing the ink solutions into a desired color. In multi-pass embodiments, dosing ink solution (S120) can be called between printing passes (e.g., a new color is dosed from an ink reservoir to the printer head).

[0128]

[0144] As part of an inkjet embodiment, depositing the ink solution (S120) may include heating the ink solution. Heating the ink solution may function to change the properties of the ink solution for printing. Heating the ink solution may be specific to the inkjet head so that the ink does not clog the head and so that jetting of the ink solution ejects droplets of a desired volume and velocity.

[0129]

[0145] As part of a pre-press color embodiment, dosing ink solutions (S120) may include mixing the ink solutions. That is, for a desired pre-press color, dosing ink solutions (S120) may include determining a combination of base colors and their respective ratios to produce the desired print color, and then combining and mixing the ink solutions in the appropriate ratios. Mixing ink solutions may vary depending on the system embodiment. In many variations, mixing ink solutions may use mixing components of the system for mixing already implemented. Since typical current printer technology does not incorporate pre-press color, additional components may need to be incorporated to mix the ink solutions. Any common mixing technique may be used. Examples of mixing techniques that may be used to mix the ink solutions include mechanical mixing, magnetic mixing, high shear mixing, ultrasonication, centrifugal mixing, or planetary mixing.

[0130]

[0146] Block S130, which includes printing passes with ink solutions, functions to print a desired pattern on a target material (substrate). In some variations (e.g., pre-printing color mixing variations incorporating a single color), printing passes with ink solutions (S130) may include printing only a single pass, in which case the desired pattern is printed directly with one or more colors. In other embodiments, printing passes with ink solutions may be called multiple times, for example, to incorporate different colors in the print, to generate new colors for post-printing coloring, and / or to generate complex designs that require multiple printing passes.

[0131]

[0147] In some variations (e.g., post-print coloring), printing a pass with ink solution (S130) may be called multiple times. In these variations, one or more colors may be printed in one pass. Depending on the embodiment, the ink solution may be allowed to dry before printing additional passes.

[0132]

[0148] Additionally or alternatively, the method may include post-print additive coloring. In additive post-print coloring, printing passes with ink solutions (S130) can print a single color or multiple colors simultaneously. To achieve the desired post print color, various color ink solutions can be deposited by additional printing passes. In contrast to subtractive post-print coloring, additional passes are printed before the ink solutions dry, thereby producing a single film on the substrate with the desired post-print color. In some variations, "mixing" techniques can be incorporated to better mix the ink solutions deposited on the substrate. Examples of post-print mixing techniques that can be incorporated include inductive mixing by magnetic fields or electrical stimulation, heating the ink solutions, or ultrasonic treatment.

[0133]

[0149] In an inkjet printing variant, printing passes with the ink solution (S130) may include setting a print speed. Setting the print speed may include setting an ink solution jetting speed and setting a printer head movement speed. The jetting speed and movement speed may depend on the particular inkjet embodiment and ink solution mixture. Preferably, the jetting speed is selected to provide an appropriate volume and velocity of ejected ink solution droplets. The print speed may further include allowing for drying times for layering multiple colors (e.g., during additive color mixing).

[0134]

[0150] In some variations, the method may include post-treating the print (S140). Post-treating the print (S140) may function to modify the print after printing. Depending on the embodiment, post-treating the print (S140) may be performed after a single printing pass, immediately after each printing pass, immediately after several printing passes, or immediately after all printing passes, after all printing is completed, or any variation thereof. Post-treating may include drying the print, blending multiple printing passes, stabilizing the print, cross-linking the print, or enhancing or modifying the print in some other way. In some variations, post-treating the print may include printing a protective overprint varnish, clear coating, or some other surface material on the print.

[0135]

[0151] In some variations, post-processing the print (S140) may include ambient drying of the print or actively drying (e.g., by use of infrared / heat or ultraviolet lamps). Actively drying the print may allow the ink solution to dry quickly to enable efficient multi-pass printing or other types of post-processing. In multi-pass embodiments, the print may be actively dried to partially or completely dry the ink solution after each pass.

[0136]

[0152] In some variations, post-processing the printing (S140) can include blending multiple printing passes (e.g., for additive post-printing coloring). This blending can be incorporated by agitation (e.g., sonication) or mechanical blending of the multiple printing passes. Blending of the multiple printing passes is preferably performed immediately after printing the passes (S130) to prevent the multiple passes from drying before being combined into a single pass.

[0137]

[0153] In another variation, post-treating the print (S140) includes stabilizing the print. Stabilizing the print can help to better protect the print from environmental and other external factors. Stabilizing the print can include applying a protective coating (e.g., applying a clear resin). In some examples, stabilizing the print can layer the ink solutions so that the colors do not mix. In some examples, stabilizing the print can include inducing a chemical change within the print.

[0138]

[0154] In some variations, the method may further include modifying the steps to enable specific operating modes. Examples of possible operating modes include print quality operating modes (e.g., high resolution printing or ink saving mode), speed operating modes (e.g., high throughput speeds or high quality printing at slower speeds), and color operating modes (e.g., color or black / white printing, or grayscale printing).

[0139]

[0155] As discussed above, the method can utilize the properties of the structured ink solution to create color designs with additive or hybrid additive / subtractive coloring. Additive coloring can be incorporated before or after printing onto the substrate, and hybrid additive / subtractive coloring can be incorporated after printing by layering the colors. The method can also incorporate any combination of pre-print additive coloring, post-print additive coloring, and post-print hybrid additive / subtractive coloring.

[0140]

[0156] For example, the system may include first obtaining two ink solutions. Through pre-printing additive coloring, the two ink solutions may be combined to form ink solutions for red, green, and blue. These colors may then be printed and post-printing coloring may be used to generate an RGB gamut design using the red, green, and blue ink solutions.

[0141]

[0157] The method is very specific to the embodiment and may include many variations depending on the printing system implemented and the desired coloring method. In one variation, a printing method for structured ink may include receiving at least one container of photonic crystal forming ink in a printer system, the photonic crystal ink containing a solution that dries to a photonic crystal film of a specified color once printed on a substrate, preparing the photonic crystal forming ink for printing by dosing the ink solution, and depositing a first layer of photonic crystal film by printing the ink solution. Depending on the embodiment, the method may further include post-treating the photonic crystal film. In one variation, post-treating the photonic crystal film includes adding a protective clear coat or overprint varnish on the photonic crystal film. In another variation, post-treating the photonic crystal film includes actively drying the photonic crystal film.

[0142]

[0158] The method may be particularly suitable for pre-printing additive color mixing. In these variations, a printing method for structured inks may include receiving at least one container of photonic crystal forming ink in a printer system, the at least one container of photonic crystal forming ink including at least two containers of photonic crystal forming ink, depositing an ink solution including mixing the photonic crystal forming inks of the at least two containers to achieve an ink solution of a desired color pre-printing and preparing an ink solution of the desired color for printing, depositing a first layer of photonic crystal film corresponding to the desired color pre-printing by printing the ink solution, and post-treating the photonic crystal film.

[0143]

[0159] Depending on the embodiment of pre-print additive color mixing, the method can incorporate coloring using a minimum of two containers. In a two-ink embodiment of pre-print additive coloring, the at least two containers of photonic crystal ink correspond to two containers, i.e., a first photonic crystal ink and a second photonic crystal ink, and mixing the photonic crystal inks of the two containers includes setting a desired pre-print color by a ratio of the first photonic crystal ink and the second photonic crystal ink.

[0144]

[0160] The method further allows for pre-print coloring using more traditional three-color additive coloring (e.g., RGB color gamut), for example, in three-container coloring, the at least two containers of photonic crystal ink include three containers of photonic crystal ink, i.e., a first photonic crystal ink (e.g., corresponding to a red ink), a second photonic crystal ink (e.g., corresponding to a green ink), and a third photonic crystal ink (e.g., corresponding to a blue ink), and mixing the photonic crystal inks of the three containers includes setting a desired pre-print color by a ratio of the first photonic crystal ink, the second photonic crystal ink, and the third photonic crystal ink.

[0145]

[0161] The method can also be adapted for post-print coloring. In a post-print coloring variation, a printing method for structured inks can include receiving at least one container of photonic crystal forming ink in a printer system, the at least one container of photonic crystal forming ink including at least two containers of photonic crystal forming ink, depositing an ink solution including depositing one photonic crystal forming ink at a time, printing an ink solution including printing multiple passes on a substrate with different photonic crystal ink solutions, and post-treating the photonic crystal film.

[0146]

[0162] As an example of additive post-printing color, printing multiple passes on the substrate includes mixing the printed ink solutions such that, once dried, only a single layer of the determined post-printing color is deposited on the substrate. As part of a "traditional" RGB embodiment of post-printing coloring, the at least two containers of photonic crystal ink include three containers of photonic crystal ink, namely, a first photonic crystal ink corresponding to red ink, a second photonic crystal ink corresponding to green ink, and a third photonic crystal ink corresponding to blue ink. Printing the ink solutions includes printing a calculated amount of the first photonic crystal ink, printing a calculated amount of the second photonic crystal ink, printing a calculated amount of the third photonic crystal ink, and mixing the photonic crystal ink solutions.

[0147]

[0163] The method can also be adapted for hybrid additive / subtractive printing. In hybrid additive / subtractive post-printing color, printing passes with ink solutions for multiple passes can include printing with different photonic ink solutions or different subtractive color ink solutions in each of the printed passes. Post-processing the photonic crystal film can then include drying the photonic crystal film and / or drying the subtractive color ink film such that, once completed, a multilayer film corresponding to the determined post-printing color is deposited on the substrate.

[0148]

[0164] Further, in some variations, the at least two containers of photonic crystal ink may include four containers of ink solutions: a first photonic crystal ink corresponding to a red ink, a second photonic crystal ink corresponding to a green ink, a third photonic crystal ink corresponding to a blue ink, and a fourth ink subtractive color ink solution (e.g., black / other color pigment or dye). In this variation, printing the ink solutions may include printing a calculated amount of the first photonic crystal ink, printing a calculated amount of the second photonic crystal ink, printing a calculated amount of the third photonic crystal ink, and printing a calculated amount of the fourth subtractive color ink, and post-processing the photonic crystal ink includes drying the layer of the first photonic crystal ink, drying the layer of the second photonic crystal ink, drying the layer of the third photonic crystal ink, and drying the subtractive color ink layer. In an alternative variation, the incorporated subtractive color ink solutions may include the entire subtractive color gamut (e.g., CMYK gamut).

[0149]

[0165] As used herein, first, second, third, etc. are used to characterize and distinguish various elements, components, regions, layers, and / or sections. These elements, components, regions, layers, and / or sections should not be limited by these terms. Numerical terms may be used to distinguish one element, component, region, layer, and / or section from another element, component, region, layer, and / or section. The use of such numerical terms does not imply a sequence or order unless the context clearly indicates. Such numerical references may be used interchangeably without departing from the teachings and variations of the embodiments herein.

[0150]

[0166] From the foregoing detailed description, together with the drawings and claims, those skilled in the art will appreciate that modifications and variations can be made to the embodiments of the invention without departing from the scope of the invention, which is defined in the following claims.

Claims

1. at least one block copolymer, at least one solvent; Equipped with Compositions for printable photonic crystal forming ink solutions.

2. The composition of claim 1 further comprising at least one co-binder.

3. The composition of claim 2 , wherein the at least one solvent comprises a reactive monomer or oligomer.

4. The composition of claim 2 , wherein the at least one solvent comprises water.

5. The composition of claim 2 , wherein the at least one co-binder comprises a crosslinking functional group.

6. The composition of claim 3, wherein the at least one co-binder comprises sucrose acetate isobutyrate (SAIB-100).

7. The composition of claim 3 , wherein the at least one co-binder comprises sucrose benzoate.

8. The composition of claim 3 further comprising a swelling agent.

9. The composition of claim 8 , wherein the swelling agent comprises crosslinking functionality.

10. The composition of claim 3 , wherein the composition has a combined dry state prior to the addition of the at least one solvent and becomes a functional printable photonic crystal forming ink solution upon the addition of the at least one solvent.

11. 1. A printing method for structure ink comprising: receiving at least one container of photonic crystal forming ink in a printer system, - receiving at least one container of photonic crystal forming ink containing a solution that, once printed on a substrate, forms a photonic crystal film of a specified color; preparing the photonic crystal forming ink for printing by depositing the ink solution; depositing a first layer of photonic crystal film by printing said ink solution; A method comprising:

12. The method of claim 11 , wherein printing the ink solution comprises depositing multiple layers of the photonic crystal film by printing multiple passes.

13. The method of claim 11 , further comprising post-treating the photonic crystal film.

14. The method of claim 13 , wherein post-treating the photonic crystal film comprises adding a protective clear coat or overprint varnish over the photonic crystal film.

15. The method of claim 13 , wherein post-processing the photonic crystal film comprises actively drying or curing the photonic crystal film.

16. receiving at least one container of photonic crystal forming ink includes receiving at least two containers of photonic crystal forming ink; - dosing the ink solution includes mixing the photonic crystal forming inks of the at least two containers to achieve a desired color ink solution before printing; printing the ink solution includes depositing a first layer of a photonic crystal film corresponding to a desired color prior to the printing; The method of claim 12.

17. the at least two containers of photonic crystal ink include two containers of photonic crystal ink, a first photonic crystal ink and a second photonic crystal ink; 17. The method of claim 16, wherein mixing the photonic crystal inks of the two containers includes setting a desired color before printing by a ratio of the first photonic crystal ink and the second photonic crystal ink.

18. The at least two containers of photonic crystal ink are comprised of three containers of photonic crystal ink, namely: a first photonic crystal ink corresponding to the red ink; a second photonic crystal ink corresponding to the green ink, and a third photonic crystal ink corresponding to the blue ink; 17. The method of claim 16, wherein mixing the photonic crystal inks of the three containers includes setting a desired color before printing by a ratio of the first photonic crystal ink, the second photonic crystal ink, and the third photonic crystal ink.

19. Because it is a post-print coloring mode, receiving at least one container of photonic crystal forming ink includes receiving at least two containers of photonic crystal forming ink; determining a printed color, the determining including calculating an amount of each photonic crystal ink required to produce the printed color; - depositing the ink solution, including depositing one photonic crystal forming ink at a time; printing different photonic ink solutions, including printing multiple passes on a substrate with said ink solutions; The method of claim 11 further comprising:

20. 20. The method of claim 19, wherein for additive post-printed colors, printing multiple passes onto a substrate includes mixing the printed ink solutions such that, once dried, only a single layer film of the determined post-printed color is deposited on the substrate.

21. The at least two containers of photonic crystal ink are comprised of three containers of photonic crystal ink, namely: a first photonic crystal ink corresponding to the red ink; a second photonic crystal ink corresponding to the green ink, and a third photonic crystal ink corresponding to the blue ink; Printing the ink solution comprises: - printing said calculated amount of said first photonic crystal ink; - printing said calculated amount of said second photonic crystal ink; - printing the calculated amount of the third photonic crystal ink; and The method of claim 20, further comprising mixing the photonic crystal ink solution.

22. 20. The method of claim 19, wherein for a hybrid additive / subtractive printed color, printing passes with ink solutions for multiple passes includes printing passes with different photonic crystal inks or different subtractive color ink solutions in each printed pass, and post-processing the photonic crystal film includes drying the photonic crystal film or drying the subtractive color ink film, such that once completed, a multilayer film corresponding to the determined printed color is deposited on the substrate.

23. The at least two containers of photonic crystal ink are a mixture of four containers of photonic crystal ink solution, namely: a first photonic crystal ink corresponding to the red ink; - a second photonic crystal ink corresponding to the green ink; a third photonic crystal ink corresponding to the blue ink; and a fourth ink comprising a subtractive color ink solution, Printing the ink solution comprises: - printing said calculated amount of said first photonic crystal ink; - printing said calculated amount of said second photonic crystal ink; - printing the calculated amount of the third photonic crystal ink; and - printing said calculated amount of said fourth subtractive color ink; Post-treating the photonic crystal film comprises: - drying the first layer of photonic crystal ink; - drying the second layer of photonic crystal ink; - drying the third layer of photonic crystal ink; and - drying the subtractive color ink layer.

24. 1. A printing system for structured inks, comprising: An ink container system including at least a first ink container, - each ink container contains a structured ink solution; an ink container system, the first ink container containing a first structural color solution, the first structural color solution including a first distinct block copolymer or a first distinct block copolymer mixture; A deposition system capable of producing a photonic crystal deposit by depositing a printing solution onto a substrate; a dosing mechanism connected to the ink container system and the deposition system, the dosing mechanism building up the printing solution once a print order is received by dosing an appropriate amount of the appropriate structural color solution into the deposition mechanism; A printing system comprising:

Images