Article with embedded pigment

Abstract

Disclosed herein is a manufactured article made by environmental reaction extrusion, the article comprising a) a hardenable composition; and b) a pigment component comprising a pigment and / or particles. When the hardenable composition is at least partially unhardened, the pigment component can be applied to at least a portion of the surface of the article such that the pigment and / or the particles are embedded after hardening.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 386,196, filed on December 6, 2022, entitled "Coatings with Embedded Pigments", and U.S. Provisional Application No. 63 / 514,226, filed on July 18, 2023, entitled "Articles with Embedded Pigments", which are hereby incorporated by reference. Technical Field

[0003] The present disclosure generally relates to articles made by ambient reaction fabrication (wherein pigments and / or particles are embedded) and methods for fabricating the same. Background Art

[0004] There is a desire to improve methods for fabricating articles and impart visual and / or other effects to such articles. Summary of the Invention

[0005] The present disclosure relates to a fabricated article made by ambient reaction extrusion, the fabricated article comprising a) a curable composition; and b) a pigment component comprising pigments and / or particles. When the curable composition is at least partially uncured, the pigment component is applied to at least a portion of the surface of the article such that the pigments and / or particles are embedded upon curing.

[0006] The present disclosure further relates to a fabricated article made by: depositing a curable composition using ambient reaction extrusion to form a three-dimensional article; applying a pigment component comprising pigments and / or particles to at least a portion of the surface of the article when the curable composition is at least partially uncured; and curing the curable composition.

[0007] Methods for fabricating such articles are also within the scope of the present disclosure.

[0008] The present disclosure also relates to a screw conveyor adapted to convey a pigment component from a auger sleeve to an auger discharge port. Brief Description of the Drawings

[0009] Figure 1a and Figure 1b Shows cross-sectional views of the three-dimensional article described herein before (1a) and after (1b) embedding pigments and / or particles as described herein.

[0010] Figure 2 Shows a cross-sectional view of the three-dimensional article described herein.

[0011] Figure 3 Scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX) images of three-dimensional articles of Example 1 samples 1-4 are shown.

[0012] Figure 4 A macroscopic image of a cross-section of a three-dimensional article of Example 2 is shown.

[0013] Figure 5 is a perspective view of a screw conveyor that can be used according to the present disclosure.

[0014] Figure 6 is a side view of a screw conveyor without a auger sleeve or auger housing that can be used according to the present disclosure.

[0015] Figure 7 is a front view of an auger that can be used for a screw conveyor according to the present disclosure. Detailed Description

[0016] The present disclosure relates to a manufactured article made by ambient reactive extrusion, the manufactured article comprising a) a curable composition; and b) a pigment component comprising a pigment and / or particles, wherein the pigment component is applied to at least a portion of the surface of the article when the curable composition is at least partially uncured such that the pigment and / or particles are embedded after curing. The present disclosure further relates to a manufactured article made by: depositing a curable composition using ambient reactive extrusion to form a three-dimensional article; applying a pigment component comprising a pigment and / or particles to at least a portion of the surface of the article when the curable composition is at least partially uncured; and curing the composition. Methods for making such articles are also within the scope of the present disclosure.

[0017] As used herein, "ambient reaction extrusion" ("ARE") and like terms refer to an additive process by which layers of materials such as curable compositions are stacked to create three-dimensional parts, such as creating three-dimensional articles by applying a layer on top of a layer of a curable or hardenable composition. ARE can use co-reactive compositions; that is, at least two components that react with each other (i.e., "co-react"). When the first co-reactive component (sometimes referred to herein as the first reactant group, the first reactive functional group, or the A part) and at least one second co-reactive component (sometimes referred to herein as the second reactant group, the second reactive functional group, or the B part) are extruded in a combined and / or continuous manner, they chemically react with each other to form a curable composition. The curable composition can then be cured or hardened under ambient conditions, or, depending on the chemistry of the reaction, cured or hardened with the aid of heating (above ambient temperature), actinic radiation, a catalyst, addition of a curing agent (after extrusion), etc., to form an article that includes a part of the manufactured article. Such compositions are referred to herein as "curable", "hardenable", or like terms because at least a portion of their polymerizable and / or crosslinkable components are capable of reacting. "Crosslinkable" means that a molecule or polymer contains functional groups that can react with the functional groups of another molecule or polymer. The terms curable, cure, harden, and like terms can be used interchangeably herein.

[0018] Similarly, "curing potential", "hardening potential", or like terms refer to the amount of reaction that can potentially occur in a composition, which is determined by the amount of reactive functional groups and (in some cases) crosslinking agents present in the composition. Thus, a curable composition that is "at least partially unhardened" means partially cured / hardened; in other words, not all of the polymerizable or crosslinkable components in the composition have reacted; and the polymerizable or crosslinkable components can continue to react. Partial curing or hardening to X% of the curing / hardening potential indicates that X mol% of the reactive functional groups present have reacted, where X represents the number of moles of reactive functional groups that have reacted divided by the total number of moles of reactive functional groups that are capable of reacting. By applying a pigment component to a composition of an article that is partially unhardened, as curing / hardening continues, the pigment and / or particles become embedded in the article.

[0019] As used herein, "embed (embed, embedded)" and like terms refer to being partially or completely surrounded within a curable composition. According to the present disclosure, pigments and / or particles can be completely embedded or only partially embedded in the curable composition.

[0020] According to the present disclosure, any curable composition suitable for ARE can be used. This broadly includes thermosetting polymers (sometimes referred to as thermosets), thermoplastic polymers, or combinations thereof. One of ordinary skill in the art selects the co-reactive components to obtain the desired curable composition and thus formulates an article.

[0021] According to the present disclosure, articles are manufactured in an additive manner by extruding a curable composition onto a surface such as a build platform. The curable composition can be in at least a partially reacted state upon extrusion and then fully reacts and cures to form a layer of the curable composition. Successive layers of the same and / or different curable compositions can be deposited to form additional material layers. The combination of the layers forms the article. The curable composition can be at least partially reacted when the co-reactive components are brought together (such as in a mixing volume) prior to extrusion. Alternatively, two co-reactive components can be pre-mixed prior to extrusion and processed in some way (such as by freezing the composition after mixing) to prevent reaction between the co-reactive components.

[0022] It may be necessary to select the chemistry of each layer of the deposited curable composition in order to form covalent bonds between successive layers. Different parts of the article can be printed using different curable compositions (e.g., printing a first curable composition to form a first part of the object, such as a base part, internal structure, etc., and then printing a second curable composition to form a second part of the object); depending on the chemical reactivity between the different curable compositions, covalent bonds can also form between the different materials.

[0023] The printed article can have rigid parts (which cannot be bent without breaking), flexible parts (which do not break when initially bent), rigid parts and foamy parts (the curable composition contains voids), tactile parts (textured) and rigid and / or flexible parts, two or more parts with different densities, one or more conductive parts, one or more thermally / electrically conductive parts (which allow heat or current to pass through), two or more different colors, two or more different rheological properties, two or more different materials with different affinities for water and / or solvents, etc. The printed article can also deposit the curable composition onto an existing article (e.g., other thermosets and / or thermoplastics, metals, wood, composites, ceramics, etc.).

[0024] Due to the covalent bonding between the printed layers, the ambient manufacturing described herein can produce objects with higher strength compared to other extruded or printed components, particularly along the Z (e.g., vertical) axis. The strong intra- and inter-layer covalent bonding not only produces stronger components but also results in a more uniform component geometry; that is, there are fewer differences in the printed lines and / or parts. Thus, the present disclosure provides the ability to form objects with multiple substrates and / or parts containing different compositions through a process.

[0025] Table 1 describes suitable curable compositions and the co-reactive components that can form them. These curable compositions can be printed by any of the methods described herein (alone or in combination) to form three-dimensional objects.

[0026]

[0027]

[0028] Many of the entries in Table 1 contain amine-containing compounds. The amine-containing compounds can include compounds sold by Covestro LLC under the trade name DESMOPHEN.

[0029] Many of the entries in Table 1 contain polyisocyanate-containing compounds. The polyisocyanate-containing compounds can include compounds sold by Covestro LLC under the trade name DESMODUR.

[0030] According to the present disclosure, the curable composition can be three-dimensionally printed at a relatively low viscosity (less than 1,000,000 cps). "Viscosity" refers to the value measured at 23 °C and ambient pressure and reflects the flow resistance of a fluid when subjected to shear stress and / or shear strain. The viscosities reported herein were measured using a Brookfield viscometer (AMETEK, Inc.) with a No. 7 rotor at 50 rpm. Thus, a relatively large amount of additives and / or fillers (e.g., a relatively high weight percentage, such as but not limited to 5 wt% based on the total weight of the curable composition) can be added to the curable components while maintaining a printable viscosity (less than 1,000,000 cps). Both the type and / or amount of the additives can be selected or "tuned" to obtain the desired chemical and / or physical properties of the printed article. The curable composition can be tuned by adding additives and / or fillers to obtain the desired mechanical properties (e.g., strength, elasticity, stiffness, sag resistance, etc.), surface properties (e.g., hardness, texture, smoothness, etc.), chemical resistance (e.g., solvent resistance, etc.), heat resistance (including flame retardancy, etc.) or thermal conductivity, and / or electrical insulation or conductivity. The curable composition can also be tuned by adding one or more catalytic / activating / promoting additive(s) to any of the curable components to obtain the desired reaction kinetics, such as the reaction rate.

[0031] Table 2 describes additives that can be included in any curable composition according to the present disclosure, such as the additives described in Table 1. Depending on the desired chemical and / or physical properties of the resulting object, the additives can be included in either or both of the first co-reactive component and the second co-reactive component. Table 2 describes specific additives and fillers applicable to three-dimensional printing based on ambient reaction extrusion, but Table 2 is not restrictive. Thus, other additives, such as additives known to those skilled in the fields of coatings, extrusion, and thermoplastics, can be included in the curable composition.

[0032]

[0033]

[0034]

[0035] Table 2 lists various additives and fillers, such as but not limited to fumed silica, such as fumed silica sold by Cabot Corporation under the trade name CABOSIL; hindered amine light stabilizers, such as hindered amine light stabilizers sold by BASF SE under the trade name TINUVIN; UV light absorbers, such as ultraviolet absorbers sold by CYTEC Industries Inc under the trade name CYASORB.

[0036] Any suitable combination of co-reactive compositions and optional additives / fillers can be printed by a three-dimensional printing system suitable for mixing and extruding raw materials. Two or more volumetric metering pumps (e.g., piston pumps, screw pumps, etc.) can discharge two co-reactive components associated with the curable composition (e.g., a first co-reactive component discharged by a first metering pump and a second co-reactive component discharged by a second metering pump) in a combined or continuous manner, respectively, and convey them to a mixing volume. In some cases, the mixing volume can include mechanical (e.g., drive) mixing characteristics. After entering the mixing volume, the first curable component and the second curable component start to mix and react, and then are extruded through an extrusion printing nozzle in an at least partially reacted state. After extrusion, the two co-reactive components further react and cure or harden.

[0037] Before applying a pigment component to the surface of the curable composition, two or more layers of the curable composition can be applied. One or more initial or first layers can have a viscosity and / or gelation high enough such that the first layer does not move significantly once applied and can be used to provide a surface onto which a second curable composition of lower viscosity can be applied. In such a case, the pigments and / or particles in the pigment composition can be more easily embedded in the second curable composition of lower viscosity, while the second curable composition remains in place through the initial first layer of higher viscosity and / or gelation.

[0038] Compared with the second curable composition that constitutes the second layer, the first curable composition that constitutes the first layer may contain a higher amount of rheological modifier and / or filler. The first curable composition may contain 1 wt.% to 15 wt.%, such as 1.5 wt.% to 10 wt.% or 2 wt.% to 5 wt.% of rheological modifier and / or filler, and the second curable composition may contain 0 wt.% to 3 wt.%, such as 0.5 wt.% to 2.5 wt.% or 0.75 wt.% to 2 wt.% of rheological modifier and / or filler, both based on the weight of the respective curable composition. The resulting rheology of the first curable composition and the second curable composition may be, but is not limited to, 1 cps to 1,000,000 cps, such as 250 cps to 500,000 cps, 300 cps to 100,000 cps or 500 cps to 50,000 cps, and this rheology is measured using a Brookfield viscometer (AMETEK, Inc.) with a No. 7 rotor at 50 rpm and 23 °C. The viscosity of the uncured first curable composition may be greater than the viscosity of the second curable composition.

[0039] The article of the present disclosure includes a pigment component, which may include pigments and / or particles. As used herein, the term "pigment component including pigments and / or particles" refers to a component applied to at least a partially uncured portion of the curable composition. The "pigments and / or particles" in the pigment component refer to components that impart visual and / or performance effects. The pigments and / or particles in the pigment component are different from the pigments, fillers, and other additives that may be included in the co-reactive components, such as those listed in Table 2.

[0040] Any type of pigments and / or particles may be included in the pigment component. As non-limiting examples, the pigments and / or particles in the pigment component may include: visual effect pigments that produce visual effects, such as color effect or color-imparting pigments, metallic pigments, luminescent pigments, (retro)reflective pigments and / or particles, performance effect pigments that produce specific performance characteristics, such as radar reflective pigments, lidar reflective pigments, conductive pigments, dielectric pigments, magnetic particles, EMI / RFI shielding particles, and / or other pigments and / or particles that impart the desired characteristics to the article.

[0041] Suitable colorant pigments are well known and include organic and / or inorganic materials such as titanium dioxide, zinc oxide, iron oxide, carbon black, carbazole dioxazine crude pigments, azo, monoazo, bisazo, naphthol AS, salt types (lakes), benzimidazolone, condensed, metal complexes, isoindolinone, isoindoline, and polycyclic phthalocyanines, quinacridone, perylene, violanthrone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylium, quinophthalone pigments, diketopyrrolopyrrole red ("DPPBO red"), monoazo red, iron oxide red, quinacridone maroon, transparent red oxide, cobalt blue, iron blue, iron oxide yellow, chromium titanate, titanium yellow, nickel titanate yellow, transparent oxidized yellow, lead chromate yellow, bismuth vanadium yellow, pre-dulled chrome yellow, transparent red oxide flakes, iron oxide red, molybdate orange, molybdate orange red, radar reflective pigments, lidar reflective pigments, corrosion inhibiting pigments, and combinations thereof.

[0042] The metallic pigments can be of any shape such as spherical, flaky or granular, and can include for example aluminum, stainless steel, zinc, copper and their alloys and their flakes; interference pigments such as titanium dioxide coated mica, muscovite, phlogopite or biotite; mica; gold, silver, nickel, platinum, bronze, brass, titanium, tungsten, including their oxides and alloys.

[0043] Luminescent pigments and (retro)reflective particles such as (retro)reflective microspheres are commercially available. As used herein, (retro)reflection and like terms refer to retroreflection or reflection. A "reflective" pigment or particle is a pigment or particle that reflects light specularly (i.e., at the same angle with respect to the normal to the pigment surface, but on the opposite side of the normal at an angle with respect to the direction of incidence of the incident light), which can include for example metallic flake pigments; or a pigment or particle that diffusely reflects or scatters light (in multiple directions), which can include for example titanium dioxide white pigment; a "retroreflective" pigment or particle is a pigment or particle that returns light to the light source, and can include for example coated glass beads. A "luminescent pigment" is an organic or inorganic compound that absorbs and releases energy in the form of visible light when they are relatively cold.

[0044] The pigments in the pigment composition may include radar reflection pigments, lidar reflection pigments, infrared reflection pigments, conductive pigments, dielectric pigments, thermally conductive electrical insulating materials, thermally conductive conductive materials, non-thermally conductive electrical insulating materials, magnetic particles, EMI / RFI shielding particles, and / or other pigments that impart desired properties to the article. Lidar, radar reflection, or infrared reflection pigments may include, but are not limited to, nickel manganese ferrite black (Pigment Black 30), chromite iron brown black (CI Pigment Green 17, CI Pigment Brown 29, and 35), Pigment Blue 28, Pigment Blue 36, Pigment Green 26, Pigment Green 50, Pigment Brown 33, Pigment Brown 24, Pigment Black 12, and Pigment Yellow 53, and combinations thereof. "Conductive pigments or particles" refer to materials that can act as a pair of electrodes or current collectors, such as conductive carbon, metals, metal oxides, graphene, or combinations thereof, and can be in various forms, such as nanoparticles, microparticles, nanowires, microwires, nanotubes, microtubes, or other forms or combinations of such forms; such particles do not necessarily provide color properties but can provide other performance properties. Dielectric pigments refer to optically variable thin film pigment flakes that can be prepared by chemically depositing a dielectric layer on a flake-shaped substrate or depositing a combination of a transparent dielectric layer, a semi-transparent metal layer, and a metal reflective layer on a vacuum flexible mesh to form a multi-layer thin film interference structure. "Magnetic pigments or particles" refer to materials having ferromagnetic, ferrimagnetic, superparamagnetic, and / or superferrimagnetic properties, such as iron, cobalt, and nickel, and their oxides and / or alloys, such as CoPt, FePt, FeNi, or FeCo, AlNiCo, CoPt, FeCoCr, and combinations thereof. "EMF / RFI shielding pigments or particles" refer to materials designed to absorb, reflect, or conduct away electronic noise from sensitive devices and circuits or around them, non-limiting examples of such materials include aluminum, copper, tin, epoxy resin, and ferrite powder, gold fabric, and nickel.

[0045] The pigments in the pigment component can include corrosion-inhibiting pigments. Any suitable corrosion-inhibiting pigments known in the art can include, for example, calcium strontium, zinc phosphosilicate; double orthophosphates, where one of the cations is represented by zinc, non-limiting examples being Zn-Al, Zn-Ca, Zn-K, Zn-Fe, Zn-Ca-Sr, Ba-Ca, Sr-Ca and combinations thereof; combinations of phosphate anions with anti-corrosion effective anions, non-limiting examples being silicates, molybdates and borates; modified phosphate pigments modified by organic corrosion inhibitors and combinations thereof. Non-limiting examples of modified phosphate pigments include aluminum(III) zinc(II) phosphate, basic zinc phosphate, zinc phosphomolybdate, zinc calcium phosphomolybdate, zinc borophosphate, zinc strontium phosphosilicate, calcium barium phosphosilicate, calcium strontium zinc phosphosilicate and combinations thereof. Other non-limiting examples of corrosion-inhibiting pigments that can be used in coating formulations include zinc 5-nitroisophthalate, calcium 5-nitroisophthalate, calcium cyanurate, metal salts of dinonylnaphthalenesulfonic acid and combinations thereof. Particularly suitable corrosion-inhibiting pigments include magnesium oxide (such as nanoscale magnesium oxide (as a non-limiting example according to ISO 13320-1 (1999), as reported by the manufacturer, determined by laser diffraction to be 5-100 nm)), micron-scale magnesium oxide (determined according to ISO 13320-1 1999 to be 1-5 microns), silicon dioxide, lithium salts (such as lithium nitrate, lithium sulfate, lithium fluoride, lithium bromide, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide) or combinations of any of these.

[0046] The median particle size of the pigments in the pigment component can range from 2-75 μm, such as 2-50 μm, 2-40 μm, 2-30 μm, 2-25 μm, 2-10 μm, 5-75 μm, 5-50 μm, 5-40 μm, 5-30 μm, 5-25 μm or 5-10 μm. As a non-limiting example according to ISO 13320-1 (1999), as reported by the manufacturer, the median particle size measured or reported herein is determined by laser diffraction.

[0047] The pigments and / or particles in the pigment component can account for 0.1-100 wt.%, such as 1-90 wt.%, 1-75 wt.% or 10-70 wt.%, these wt.% being based on the total weight of the pigment component. The pigments and / or particles can account for 100% of the pigment component, such as dry pigment particles. The pigment component can be in the form of a slurry of the pigments and / or particles in a suitable slurry medium. The slurry medium can be selected based on the type of pigments and / or particles used, the type of the curable composition to which the pigment component is to be applied and / or the application method of the pigment component. The pigment component can also be in the form of a "rinsing liquid" or "dipping liquid". Non-limiting examples of suitable media for forming the slurry or rinsing liquid include water; C3-C 12Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as isopropyl alcohol, butanol, and 2-ethylhexanol; monomethyl ethers, monoethyl ethers, and monohaxyl ethers of ethylene glycol or propylene glycol such as propylene glycol methyl ether; C2-C 12 Aldehydes such as acetaldehyde, cinnamaldehyde, and vanillin; esters such as ethyl acetate, butyl acetate, phthalate, sebacate, adipate, terephthalate, dibenzoate, glutarate, or azelate; or any combination thereof. "Slurry", "rinse solution", and "impregnation solution" may be used interchangeably herein as they all contain pigments and / or particles in a carrier; a slurry generally refers to a higher solids content than a rinse solution or an impregnation solution.

[0048] When the pigment component contains particles, the particles may include (by way of non-limiting example) beads, which may include glass; metals such as aluminum, stainless steel, and copper; minerals; and / or plastics such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride. The particles are generally larger in size than the pigments. As an example, when the particles are beads, the beads may have an average particle size of 76 μm to 1,500 μm, such as 80 μm to 1,400 μm, 90 μm to 1,250 μm, or 100 μm to 1,000 μm as determined according to ASTM D1214-10(2020) or AASHTO M247-81(1996). As another indicator of particle size, when the particles are beads, the particle size can be described as: 80 to 100 wt.% of the beads pass through a 12-mesh US sieve and / or 70 to 100 wt.% of the beads pass through a 14-mesh US sieve and / or 60 to 95 wt.% of the beads pass through a 16-mesh US sieve and / or 5 to 60 wt.% of the beads pass through an 18-mesh US sieve and / or 0 to 10 wt.% of the beads pass through a 20-mesh US sieve as determined according to ASTM D1214-10(2020) or AASHTO M247-81(1996).

[0049] The pigments and / or particles used in this pigment component may be pigments and / or particles that are generally incompatible with the use of ARE. For example, the pigments and / or particles may be too large to pass through the nozzle of the ARE device or may have an adverse reaction with the curable composition.

[0050] An advantage of the present disclosure is that an effect (such as a visual effect) can be achieved, wherein the amount of pigment and / or particles required to achieve the effect can be significantly lower than when it is blended into a hardenable composition. This not only allows the use of less pigment or particles, but also enables better distribution and / or alignment of the pigment or particles. For example, if the pigment includes a flake pigment, such as an aluminum flake pigment (available from Palmer Holland Inc. or Merck KGaA as a non-limiting example), better orientation of the flake pigment can be achieved; and less flake pigment can be used to achieve a better visual effect. As used herein, the term "dynamic" or "dynamic index" refers to a measurement of the change in reflectivity of a coated substrate as it rotates through a range of viewing angles, measured using a BYK-Maci spectrophotometer from BYK Co. The dynamic index for a solid color coating or a surface that does not contain a metallic pigment is typically 0, while a coating containing a metallic or pearlescent pigment typically has a dynamic value that can be considered high or low depending on the type of pigment. For example, opaque pigments typically produce coatings with low dynamics, while coatings with transparent and / or metallic pigments have high dynamics (15-17). As a non-limiting example, the hardened articles described herein can have a dynamics index greater than or equal to 8, such as greater than or equal to 10 or from 8 to 22, such as from 10 to 20. The dynamics index is a unitless value.

[0051] As described above, the pigment component is applied to the "at least partially unhardened" hardenable composition. The pigment component can be applied when the degree of hardening / curing of the hardenable composition does not exceed 75%, such as not more than 65% or not more than 50% or 0 to 75%, such as 0 to 65% or 0 to 50%, of the curing / hardening potential of the hardenable composition as described above. Thus, the pigments and / or particles in the pigment component are embedded in the composition after hardening.

[0052] Pigment component can be applied by any means known in the art, such as spraying, flushing, dipping, vibration discharge, screw conveyor and / or auger.Alternately, or in combination with any one of these methods, pigment component can be applied thereon or on the surface of the substrate or mold whereon a hardenable composition is applied.In this way, when article forms and composition hardens, the pigment and / or particle in the pigment component are embedded in the hardenable composition.Pigment component can be applied with a predetermined pattern or shape.For example, pigment component can be applied after applying hardenable composition with a motor (such as a stepper motor attached to pigment and / or particle storage device) being used.The rotational frequency of motor can be used for controlling the mass flow rate of the particles flowing out of the storage device caused by vibration amount and vibration.

[0053] Figure 5 , Figure 6 and Figure 7Shows a non - limiting example of an auger or screw conveyor that can be used to apply a pigment composition according to the present disclosure. The screw conveyor 300 includes a screw sleeve 305, a screw sleeve opening 308, a screw discharge port 310, a funnel 313, a motor 315 (such as a stepper motor), a motor housing 318, a screw housing 350, and a screw 320. The pigment composition can be fed into the screw sleeve 305 via the screw sleeve opening 308, conveyed using the screw 320, and finally discharged via the screw discharge port 310. To control and precisely place the pigment composition, the funnel 313 can be attached to the screw discharge port 310, with the narrow end of the funnel located near the previously applied curable composition.

[0054] The screw sleeve 305 acts as a hopper, and its discharge end is in fluid communication with the screw 320. The speed of the screw 320 can be controlled by the motor 315, and the motor controls the rate at which the pigment composition is discharged from the screw discharge port 310. As shown, the motor 315 is partially located within the motor housing 318 and partially exposed behind the motor housing 318.

[0055] As Figure 7 shown, the screw 320 (indicated by 335) can be 2 cm to 15 cm long, such as 3 cm to 14 cm long or 4 cm to 13 cm long. The screw 320 includes threads 340 that spiral around the axis 345 of the screw 320. The rotational movement of the screw 320 is driven by the motor 315, enabling the threads 340 to convey the pigment composition from the discharge port of the screw sleeve 305 to the screw discharge port 310.

[0056] Depending on the nature of the pigment composition, there is a spacing (indicated by 330) between the threads 340 of the screw 320, and it has a width 325 that can extend from the screw axis 345 to the inner wall of the screw housing 350 ( Figure 5 ). The width 325 of the screw 320 can be 0.2 cm to 2.5 cm, such as 0.25 cm to 2 cm or 0.3 cm to 1.5 cm. The width 325 can vary based on the nature of the pigment composition, such as the pigment and / or the particle size of the particles contained therein and the required feed rate. The spacing 330 of the screw threads 340 can be 0.5 cm to 4 cm, such as 0.75 cm to 3.5 cm or 1 cm to 3 cm. The spacing 330 can vary based on the nature of the pigment composition, such as the pigment and / or the particle size of the particles contained therein and the required feed rate.

[0057] The feed rate of the pigment component from the screw conveyor 300 to the surface of the curable composition can also be controlled by the motor 315 through the rotational speed of the auger 320. The rotational speed of the auger 320 can be from 1 rpm to 180 rpm, such as from 25 rpm to 150 rpm, or from 50 rpm to 125 rpm. The rotational speed of the auger 320 can vary based on the properties of the pigment component, such as the particle size of the pigment and / or the particles contained therein and the desired feed rate.

[0058] Particularly suitable for use in the article are those pigments and / or particles that impart a visual effect to the manufactured article. It is to be understood that coating or applying to an article made by ARE can be challenging. Embedding the pigments and / or particles directly into the surface of the curable composition forming the article avoids these challenges and can result in a high-quality finished surface. Similarly, embedding performance pigments and / or particles in the surface of the article can improve performance, such as conductivity, compared to dispersing such pigments and / or particles throughout the curable composition. The pigments and / or particles in the pigment composition are embedded in the article and no topcoat is required to keep the pigments and / or particles in place. Although a topcoat or other layer can be applied, use of such a layer can be explicitly excluded according to the present disclosure.

[0059] The curable composition can be applied with a texture that aids in the orientation of the pigments and / or particles to provide higher reflectivity or retroreflectivity. The texture can include indentations and / or "peaks and valleys", where the height difference between the peaks and valleys aids in the orientation of the pigments and / or particles.

[0060] In addition, as described above, a first curable composition can be applied to form a "checkerboard" surface. As described above, a second curable composition can be applied to the surface of the first curable composition, on which the pigment component can be applied. The rheology of the uncured first curable composition enables it to remain in place, and the rheology of the uncured second curable composition enables the pigments and / or particles in the pigment component to be embedded in the second curable composition before curing or hardening.

[0061] According to the present disclosure, the articles described herein can form all or part of a manufactured article. Specific examples include structures, vehicles, industrial protective structures (such as distribution box enclosures, transformer housings, or motor control enclosures); rail vehicle containers, tunnels, oil or gas industry components (such as platforms, pipelines, storage tanks, ships, and their supports), ship components, automotive body parts, aerospace components, pipelines, storage tanks, road surfaces, road markings, or wind turbine components. As used herein, "structure" refers to components of buildings, bridges, oil derricks, oil platforms, water towers, transmission line towers, support structures, wind turbines, walls, bridge piers, docks, levees, dams, shipping containers, trucks, and modular housings. As used herein, "vehicle" in its broadest sense refers to all types of vehicles, such as but not limited to cars, trucks, buses, tractors, harvesters, heavy equipment, vans, golf carts, motorcycles, bicycles, rail cars, airplanes, helicopters, ships of all sizes, etc.

[0062] The pigments and / or particles in the pigment component can be distributed substantially uniformly on the surface or a part of the surface of the article, and can provide a substantially uniform visual effect to the surface of the article. As used in this context, "substantially" means that the visual effect appears uniform to the naked eye. The visual effect can be, for example, a metallic visual effect, a color effect, a luminescent effect, and / or a (retro)reflective effect. The pigments and / or particles can be distributed substantially uniformly over the entire surface (100% of the surface), most of the surface (99 - 50% of the surface), a part of the surface (49 - 1% of the surface), and / or can be distributed on the surface in a predetermined pattern or shape. The pigments and / or particles can be embedded in the hardened composition such that each pigment and / or particle is surrounded by the composition, thereby being isolated from each other. Alternatively, the pigments and / or particles can be in contact with each other. This may be particularly important if conductivity is required, for example.

[0063] The pigment component and / or the hardened article can be substantially free (less than 5 weight percent based on the total weight of the article), essentially free (less than 1 weight percent based on the total weight of the article), and / or completely free (undetectable) of wear-resistant particles, conductive particles, reinforcing particles, and / or magnetic particles, and when the film-forming component is free of thermoplastics, the pigment component and / or the hardened article can be substantially free, essentially free, and / or completely free of (retro)reflective particles and / or luminescent particles.

[0064] As used herein, the term "abrasion-resistant particle" refers to fine particles that impart abrasion resistance and scratch resistance, and can include (as non-limiting examples) diamond; crystalline materials such as polycrystalline materials, single-crystalline materials, or combinations thereof; amorphous materials; ceramic materials; glass-ceramic materials; superabrasives; minerals; carbon-based materials; or any combination thereof. These particles may or may not provide additional properties. As used herein, "reinforcing particle" and like terms refer to particles that impart structural integrity (such as stiffness or strength) to a composition. Such particles can have a variety of different shapes, such as spherical, hemispherical, flake-shaped, rod-shaped, whisker-shaped, etc., and can include, for example, glass fibers and glass beads.

[0065] A continuous portion or layer of an article can be formed by depositing at least two co-reactive components onto a substrate and then depositing an additional portion or layer of a curable composition onto the underlying deposited portion or layer, thereby producing a three-dimensional article according to the present disclosure. The layers are continuously deposited to build the printed article. The curable components can be mixed and then deposited or can be deposited separately. When deposited separately, the components can be deposited simultaneously, sequentially, or simultaneously and sequentially.

[0066] The curable composition can be cured or solidified by any suitable method, such as thermal curing, radiation curing, or by reaction at ambient temperature or elevated temperature (such as but not limited to greater than or equal to 80 °C).

[0067] Figure 1a and Figure 1b Depicts a cross-section of a manufactured article according to the present disclosure. Figure 1a Shows a curable composition 100 deposited on a surface 130, and before embedding pigments and / or particles, the curable composition includes an outer surface portion 110, a surface deposition portion 120, and an inner portion 140. As Figure 1b shown, pigments and / or particles 150 are partially embedded in the outer surface portion 110. For example, this can be achieved by applying pigments and / or particles 150 after the curable composition 100 has been applied to the surface 130 (but not fully hardened or cured at this time as described herein).

[0068] Figure 2 Depicts a cross-section of a manufactured article according to the present disclosure. The article 200 includes an outer surface 210 and a core 220. As shown, the surface 210 accounts for approximately 20% of the volume of the article. Pigments and / or particles 230 from a pigment component are embedded in the outer surface 210. As described above, the pigments and / or particles can be partially and / or fully embedded, although in Figure 2is shown only as partially embedded; that is, as determined by cross-sectional microscopy, the amount of embedding of the pigment and / or particles can be from 10 vol.% to 100 vol.%, such as from 20 vol.% to 100 vol.%, or from 50 vol.% to 100 vol.%, or from 70 vol.% to 100 vol.%. Additionally, although Figure 2 shows the amount of embedding of the pigment and / or particles applied to all four outer surfaces, the pigment and / or particles can be embedded in less than the entirety of the surface, such as only one side or a portion of one side of the article 220.

[0069] Reference Figure 1b and Figure 2 , the pigment and / or particles can be concentrated in: at least 0.1 wt.% of the surface of the article, such as at least 1 wt.%, at least 5 wt.%, and can be up to 75 wt.% or greater, such as 80 wt.% or greater, 85 wt.% or greater, 90 wt.% or greater or 95 wt.% or greater. Additionally, based on the total volume of the article, the pigment and / or particles can be concentrated in at least 0.01 vol.% of a portion of the article, such as at least 0.1 vol.%, at least 1 vol.% or at least 5 vol.%, and can be up to at least 25 vol.%, such as at least 15 vol.% or at least 10 vol.%; such as Figure 1b the outer portion 110 in Figure 2 and the surface 210 in

[0070] It should be understood that the present disclosure can assume various alternative variations and sequences of steps, unless explicitly specified to the contrary. Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by application of ordinary rounding techniques.

[0071] Although the numerical ranges and parameters setting forth the broad scope of the present disclosure can be approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in its corresponding testing measurements.

[0072] Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Similarly, a range of "0.06 to 0.25 wt.% or 0.06 to 0.08 wt.%" will include each of 0.06 to 0.25 wt.%, 0.06 to 0.08 wt.%, and 0.08 to 0.25 wt.%.

[0073] Unless otherwise indicated, plural encompasses singular and vice versa. As used herein, the terms "comprising", "such as", "for example" and similar terms mean "including but not limited to", "such as but not limited to", "for example but not limited to". Similarly, as used herein, the terms "on", "applied on / onto", "formed on / onto", "deposited on / onto", "overlapped", and "provided on / onto" mean formed, overlapped, deposited or provided on a surface but not necessarily in contact with the surface. For example, an article "formed on" a substrate does not exclude the presence of one or more other articles of the same or different compositions between the formed article and the substrate.

[0074] As used herein, the articles "a", "an", and "the" include plural referents unless explicitly and unambiguously limited to one referent, and shall be construed to include "at least one" and "one or more". Thus, references to "an" article, "a" pigment and / or particle, etc. refer to one or more of these items.

[0075] Unless otherwise indicated, the ambient conditions of temperature and pressure are ambient temperature (20 °C - 25 °C) and standard pressure of 101.3 kPa (1 atm).

[0076] As used herein, the terms "auger conveyor" and "screw conveyor" refer to a mechanism that uses a rotating screw blade that may be located within a tube to convey pigment components to the surface of a curable composition.

[0077] As used herein, the transitional term "comprising" (and other comparable terms such as "containing" and "including") is "open-ended" and may include unspecified matters. Although described in terms of "including", the terms "consisting essentially of" and "consisting of" are also within the scope of this disclosure. As used herein, "consisting essentially of" means the named specified materials or steps and materials or steps that do not materially affect the basic characteristics of the disclosure; "consisting of" means only the named specified materials or steps.

[0078] As used herein, terms such as "crosslinking agent", "crosslinked product", "curing agent", "hardening agent", etc. refer to molecules or polymers containing functional groups that can react with the functional groups of polymers and / or resins in a curable composition.

[0079] As used herein, the prefix "poly" means two or more. As a non-limiting example, polyisocyanate refers to a compound containing two or more isocyanate groups, and polyol refers to a compound containing two or more hydroxyl groups.

[0080] As used herein, the term "polyisocyanate" refers to blocked (or capped) polyisocyanates as well as unblocked polyisocyanates.

[0081] As used herein, the term "polymer" includes homopolymers (formed from one monomer) and copolymers formed from two or more different monomer reactants or containing two or more different repeating units. In addition, the term "polymer" includes prepolymers and oligomers. "Polymer" and "resin" may be used interchangeably herein.

[0082] As used herein, "multi-component" (which may be "two-component" or "2K") and similar terms refer to a composition that includes a first component containing a functional material and at least one other component containing a functional material that can react with the functional material in the first component. Generally, the components are stored separately before use and react when mixed.

[0083] As used herein, terms such as "reflection" and similar terms refer to pigments and particles sending incident radiation (as a non-limiting example, light) away from the pigments or particles in a direction different from the angle of incidence of the radiation. As a non-limiting example, a mirror is considered to be reflective.

[0084] As used herein, terms such as "retroreflection" and similar terms refer to pigments and particles sending incident radiation (as a non-limiting example, light) away from the pigments or particles in the same direction as the angle of incidence of the radiation. As a non-limiting example, glass beads and prisms are considered to be retroreflective.

[0085] As used herein, terms such as "(retro)reflection" and similar terms refer to either or both of reflectivity and retroreflectivity.

[0086] As used herein, the term "vibratory discharge" refers to applying pigments and / or particles to a curable composition by causing the pigments and / or particles to flow out of a reservoir by relying on vibration (such as using the rotational frequency of a motor to adjust the amount of vibration so that the pigments and / or particles flow out of the reservoir).

[0087] As used herein, unless otherwise specified, the term "visual effect" refers to the color, metallic appearance, luminescent appearance, glitter appearance, dynamic index, and / or (retro)reflective effect imparted when pigments, dyes, and / or particles are embedded in the surface of a manufactured article.

[0088] Examples

[0089] The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way.

[0090] Example 1 - Polyurea surface embedded with effective pigments

[0091] In this example, a 3D-printable 2K polyurea formulation was printed and effect pigments were embedded in the surface. Color evaluation was performed using a BYK-Mac I metallic color spectrophotometer instrument manufactured by BYK-Gardner. The dynamic index, color, and sparkle characteristics were measured using a BYK-Mac spectrophotometer. SEM micrographs were collected to determine the orientation of the embedded particles. The 2K formulation contains a first component (containing diamine) and a second component (containing aliphatic polyisocyanate).

[0092] The components of the first component (diamine) were weighed into a Max 300L DAC cup from Flacktek. The formulation was dispersed via a typical Speedmixer procedure.

[0093] The components of the second component (aliphatic polyisocyanate) were weighed into a Max 300L DAC cup from Flacktek. The formulation was dispersed via a typical Speedmixer procedure.

[0094] The two components were transferred from the DAC cup to an Optimum dispensing head via a Flacktek SpeedDisc for 3D printing via ambient reactive extrusion using a Viscotec 2k extruder mounted on a gantry. The first and second components were printed at a volume mixing ratio of 1.2:1.

[0095] A thin sample sized 3" x 5" x 0.078" was printed from the formulation onto a Powercron 8000 panel (ACT part number 44049). The printing settings were: flow rate 3 mL / min, bead width and height 1 mm, 100% linear fill, one perimeter, speed F2400, feed rate 100%, and nitrogen pressure on the material supply tube 90 psi. After printing the sample material, the effect pigments were embedded in the 3D-printed polyurea via spray application. After particle embedding, the sample was baked at 160°F for 2 days.

[0096] The procedure for embedding particles by spraying solvent slurries or electrostatically spraying powders is summarized below, along with a summary of the relevant data in Table 3. The spraying conditions for applying the slurry were as follows: gun - 3M Accuspray, 1.2 mm nozzle, 40 psi back pressure, 21.1 °C, and 51.7% relative humidity. The powder was electrostatically sprayed by adding the powder to a cup and then applying it electrostatically (via an Encore LT manual electrostatic spray gun) to the part at a flow rate of 30 psi and an atomization pressure of 30 psi using 75 kV.

[0097] Table 3: Effect pigments embedded on the surface of 3D printed polyurea articles and their application conditions

[0098]

[0099] 1 TCR 3040, sold by Palmer Holland Inc.

[0100] 2 T60 - 23 SW, sold by Merck KGaA

[0101] The cured samples were imaged using a digital camera. Compared to Sample 1 without pigment, color changes due to the addition of effect pigments were observed, with the color changes being silver (Samples 2 and 3) or blue (Sample 4).

[0102] The cured samples were imaged using a scanning electron microscope (SEM) and energy - dispersive X - ray spectroscopy (EDX). In Figure 3 , it can be seen that the flakes are concentrated on the surface to maximize their visual effect. The corresponding EDX images confirmed the location of the pigments.

[0103] The dynamic index of the polyurea articles was measured using a BYK - Maci spectrophotometer from BYK Co. Specifically, the dynamic index was calculated by measuring the luminance (L*) of the reflected light at 15°, 45°, and 110° angles relative to the surface of the printed article and then substituting these values into Equation 1:

[0104] Equation 1

[0105] where

[0106] L* 15° = luminance of the reflected light measured at a 15° angle

[0107] L* 45° = luminance of the reflected light measured at a 45° angle

[0108] L* 110° = luminance of the reflected light measured at a 110° angle

[0109] The dynamic index of an object surface without metal particles is zero.

[0110] In the corresponding BYK Mac data, silver was observed to have the required high mobility in the L* value, indicating that the flakes are highly oriented. For xirallic pigments, both the L* and blue values show migration due to the blue added to the flakes themselves.

[0111] Table 6: Color values measured at each corner

[0112]

[0113] For Examples 2 - 4, the pigments seem to be able to penetrate the unhardened polyurea and arrange as needed to obtain the desired appearance. Adding solvent seems to enable the 3D printing resin to achieve preferential arrangement of the pigments thermodynamically; the influence of the embedding time is less significant compared to the gel time.

[0114] Example 2 - Polyurea surface embedded with glass beads

[0115] In this example, a printed 2K polyurea formulation was manufactured using ambient reactive extrusion (ARE), and solid effect particles (i.e., glass beads) were embedded in the unhardened composition. Macroscopic images were used to verify the degree of bead embedding in the material. DELTA LTL-X Mark II (part of DELTA-FORCE Technology) measurements were performed to characterize the retroreflectivity of the samples.

[0116] The 2K formulation contains a first component (containing diamine) and a second component (containing aliphatic polyisocyanate). The components of the first component were weighed into a Max 300L DAC cup from Flacktek. The formulation was dispersed via a typical Speedmixer procedure. The components of the second component were weighed into a Max 300L DAC cup from Flacktek. The formulation was dispersed via a typical Speedmixer procedure.

[0117] The second component and the first component were printed in a volume ratio of 2:1 and fed through a static mixing nozzle.

[0118] A reservoir of Potters Type III glass beads (Potters Industries LLC) was fixed to the extruder. The bottom of the reservoir had a 1 / 8” hole leading to a 1 / 4” polyurethane tube that was routed down the length of the extruder and attached to the tip of the static mixing nozzle.

[0119] A stepper motor with an eccentric weight fixed on its shaft is attached to the glass bead reservoir. The rotation frequency of the motor is controlled to adjust the vibration amount and the mass flow rate of the glass beads flowing out of the reservoir caused by the vibration.

[0120] An approximately thin rectangular sample with dimensions of 150 mm x 700 mm x 1 mm is printed, and the stepper motor vibrates to cause the glass beads to flow onto the surface of the second component. Approximately half of the radius of the glass beads is embedded in the printed second component. The embedding amount of the glass beads is verified by using the macroscopic image of the cross-section of the printed sample ( Figure 4 ). The retroreflectivity of the sample measured using DELTA LTL-XMarkII is 250 millicandela.

[0121] Example 3 - Polyurea surface embedded with glass beads applied to a road surface

[0122] In this predictive example, the curable composition described in Example 2 is directly printed onto the road surface from a truck carrying an extruder (similar to the extruder shown Figures 5 to 7 ), a printing shaft for linear drive, and the individual components of the formulation. The glass beads are embedded in the unhardened composition. An instrument such as DELTA LTL–X Mark II (part of DELTA-FORCE Technology) can be used to characterize the retroreflectivity of the sample.

[0123] The amine and isocyanate components used in the preparation of the standard polyurea formulation are prepared and transferred to a ViscoMT-XS bucket loader (ViscoTec America, Inc.), which is suitable for 3D printing by ambient reactive extrusion using a Viscotec 2k extruder (ViscoTec America, Inc.). The extruder is mounted on a slide rail at the rear of the truck, 1 cm above the road. The isocyanate composition and the amine composition are printed in a volume ratio of 2:1 and fed through a static mixing nozzle.

[0124] A reservoir of Potters Type III glass beads (Potters Industries LLC) can be fixed to the extruder. The funnel at the discharge port of the extruder leads to a 1 / 4” polyurethane tube, which is guided downward along the length of the extruder and attached to the tip of the static mixing nozzle.

[0125] The extruder can include a stepper motor with an eccentric weight fixed on its shaft and is adapted to receive the glass beads from the glass bead reservoir. The rotation frequency of the motor is used to control and adjust the vibration amount and the mass flow rate of the glass beads flowing out of the reservoir caused by the vibration.

[0126] As the truck moves forward, the extruder moves back and forth at a speed proportional to the speed of the truck. The uncured composition is allowed to penetrate into the road surface and adhere thereto. At the same time, glass beads from a reservoir fall onto the uncured material and become embedded therein after the composition hardens. After curing at room temperature, the retroreflectivity of the sample is expected to be 250 millicandela as measured above.

[0127] Example 4 - Textured polyurea surface embedded with glass beads

[0128] In this example, ambient reactive extrusion (ARE) is used to fabricate and solid effect particles (i.e., glass beads) are printed in a checkerboard pattern for a 2K polyurea formulation. The glass bead particles are embedded into the uncured composition. Confocal laser scanning microscopy is used to verify the degree of embedding of the beads in the material. DELTA LTL-X Mark II measurements are performed to characterize the retroreflectivity of the sample.

[0129] Two 2K formulations (Formulation A and B) contain a first component (containing diamine) and a second component (containing aliphatic polyisocyanate). The components of the first component are weighed into a Max 300L DAC cup from Flacktek. The formulation is dispersed via a typical Speedmixer procedure. The components of the second component are weighed into a Max 300L DAC cup from Flacktek. The formulation is dispersed via a typical Speedmixer procedure. Formulation A is prepared with 3% fumed silica, while Formulation B is prepared with 1% fumed silica. The first component of Formulation A has a viscosity of 30,000 cps and the second component has a viscosity of 20,000 cps. The first component of Formulation B has a viscosity of 13,000 cps and the second component has a viscosity of 5,000 cps. The viscosity is measured at ambient temperature (23 °C) using a Brookfield viscometer (AMETEK, Inc.) with a No. 7 rotor at 50 rpm.

[0130] The second component and the first component of the two formulations are printed at a volume ratio of 2:1 and fed through a static mixing nozzle.

[0131] The first article is printed with Formulation A. The first layer is applied to form a rectangle 12 inches (30.5 cm) by 5 inches (12.7 cm) with a thickness of 1.5 mm. The first layer consists of 1 inch (2.5 cm) by 1 inch (2.5 cm) checkerboard squares to form the first article.

[0132] A reservoir for Potter Type III glass beads is fixed to the extruder. The holes at the bottom of the reservoir guide the beads to a screw conveyor powered by a stepper motor, similar to Figure 5 , Figure 6 and Figure 7As shown. The rotational frequency of the stepper motor is used to control the mass flow rate of the beads from the reservoir or the auger sleeve. The auger rotates at approximately 90 rpm. The screw conveyor feeds the beads through a funnel into a 1 / 4” tube that guides the beads to the tip of the static mixing nozzle.

[0133] On top of the first article, formulation B is printed with the screw conveyor activated. The extruder follows the tool path above the first article, moving stepwise along the long axis of the first article and back and forth along the short axis of the article, thereby forming a layer on the top surface of the first article. Approximately half of the radius of the glass beads is embedded in formulation B of the printed material. The amount of glass bead embedding in the printed sample is verified by using confocal laser scanning microscopy. The final article (including formulation A, formulation B, and glass beads) is allowed to cure overnight under ambient conditions. The retroreflectivity of the sample measured using a DELTA LTL-X Mark II is 520 millicandela.

[0134] Although specific embodiments of the present disclosure have been described above for purposes of illustration, it will be apparent to those skilled in the art that various modifications can be made to the details of the present disclosure without departing from the scope defined in the appended claims.

Claims

1. An article of manufacture made by ambient reactive extrusion, comprising a) a curable composition; and b) a pigment component comprising pigments and / or particles; wherein when the curable composition is at least partially uncured, the pigment component is applied to at least a portion of the surface of the article such that the pigments and / or the particles are embedded upon curing.

2. An article of manufacture made by depositing a curable composition using ambient reactive extrusion to form a three-dimensional article; when the curable composition is at least partially uncured, applying a pigment component comprising pigments and / or particles to at least a portion of the surface of the article; and curing the curable composition.

3. The article according to claim 1 or 2, wherein the pigments and / or the particles in the pigment component are incompatible with ambient reactive extrusion.

4. The article according to any one of the preceding claims, wherein the pigments and / or the particles are concentrated at: at least 0.1 wt.% of the surface of the article, such as 1 wt.%, at least 5 wt.%, and up to 75 wt.% or more, 80 wt.% or more, 85 wt.% or more, 90 wt.% or more, or 95 wt.% or more; and / or based on the total volume of the article, at least 0.01 vol% of a portion of the article, such as 0.1 vol.%, at least 1 vol.%, at least 5 vol.%, and up to at least 25 vol.%, such as up to at least 15 vol.%, or up to at least 10 vol.%.

5. The article according to any one of the preceding claims, wherein the pigments and / or the particles are distributed substantially uniformly on the surface or a portion of the surface of the article and provide a substantially uniform visual effect to the surface of the article, such as a metallic visual effect, a color effect, a luminescent effect, and / or a (retro)reflective effect, and wherein the pigments and / or the particles are distributed substantially uniformly over all (100%) of the surface, most (99 - 50%) of the surface, some (49 - 1%) of the surface, and / or can be distributed on the surface in a predetermined pattern.

6. The article according to any one of the preceding claims, wherein the pigments and / or the particles comprise less than 25 wt.% of the weight of the cured article, such as less than 20 wt.%, less than 15 wt.%, less than 10 wt.%, or from 1 wt.% to 25 wt.%.

7. The article according to any one of the preceding claims, wherein the pigment component comprises dry pigments and / or particles, slurries of pigments and / or particles, and / or liquid carriers such as liquid carriers comprising water and / or organic solvents, or wash liquors comprising pigments and / or particles dispersed in carriers such as carriers comprising water and / or organic solvents.

8. The article according to any one of the preceding claims, wherein the median particle size of the pigment in the pigment composition ranges from 2 to 75 μm, such as 2 to 50 μm, 2 to 40 μm, 2 to 30 μm, 2 to 25 μm, 2 to 10 μm, 5 to 75 μm, 5 to 50 μm, 5 to 40 μm, 5 to 30 μm, 5 to 25 μm or 5 to 10 μm; wherein the median particle size is measured by laser diffraction according to ISO 13320-1 (1999).

9. The article according to any one of the preceding claims, wherein the pigment and / or the particles are embedded in the article such that, as determined by cross-sectional microscopy, based on the volume of the pigment and / or the particles, 10 vol.% to 100 vol.%, such as 20 vol.% to 100 vol.%, or 50 vol.% to 100 vol.% or 70 vol.% to 100 vol.% of the pigment and / or the particles are embedded in the article.

10. The article according to any one of the preceding claims, wherein the pigment and / or the particles have a visual effect and / or a performance effect, such as a corrosion-inhibiting pigment, a colorant pigment, a metallic pigment, a radar-reflective pigment, a lidar-reflective pigment, a filler pigment, a luminescent pigment, a (retro)reflective pigment or a combination thereof, such as a metallic-effect pigment in any shape such as spherical, flaky or granular, such as aluminum, stainless steel, zinc, copper and their alloys and their flakes, an interference pigment, such as mica coated with titanium dioxide, corundum flakes, muscovite, phlogopite or biotite, mica, gold, silver, nickel, platinum, bronze, brass, titanium, tungsten, including their oxides and alloys.

11. The article according to any one of the preceding claims, wherein the particles comprise beads, wherein the beads comprise glass, metal, mineral and / or plastic, and wherein the beads have an average particle size of 76 μm to 1,500 μm, such as 80 μm to 1,400 μm, 90 μm to 1,250 μm or 100 μm to 1,000 μm as determined according to ASTM D1214-10 (2020) or AASHTO M247-81 (1996).

12. The article according to any one of the preceding claims, wherein the particles comprise beads, and wherein 80 to 100 wt.% of the beads pass through a 12-mesh US sieve and / or 70 to 100 wt.% of the beads pass through a 14-mesh US sieve and / or 60 to 95 wt.% of the beads pass through a 16-mesh US sieve and / or 5 to 60 wt.% of the beads pass through an 18-mesh US sieve and / or 0 to 10 wt.% of the beads pass through a 20-mesh US sieve as determined according to ASTM D1214-10 (2020) or AASHTO M247-81 (1996).

13. The article according to any one of the preceding claims, wherein the pigment component and / or the cured article is substantially free of, essentially free of, and / or completely free of wear-resistant particles, conductive particles, reinforcing particles, and / or magnetic particles, and when the film-forming component does not contain a thermoplastic, the pigment component and / or the cured article is substantially free of, essentially free of, and / or completely free of retroreflective particles and / or luminescent particles.

14. The article according to any one of the preceding claims, wherein the pigment comprises flaky pigments, and the article has a dynamic index greater than or equal to 8, such as greater than or equal to 10 or from 8 to 22, such as from 10 to 20, the dynamic index being calculated by measuring the brightness of the reflected light at 15°, 45°, and 110° viewing angles relative to the surface, the surface showing the change in the reflectance of the article as the article rotates through the viewing angles.

15. The article according to any one of the preceding claims, wherein the article forms at least a part of a vehicle, a manufactured article, a consumer electronic device, a consumer appliance, a sidewalk, a road marking, or a structure, such as a component of a modular housing.

16. The article according to any one of the preceding claims, wherein the curable composition is a thermosetting plastic and comprises a first reactive component and a second reactive component, wherein: the first reactive component comprises a polyisocyanate, such as a polyisocyanate prepolymer, a bifunctional polyisocyanate prepolymer, an isocyanate-terminated polytetramethylene prepolymer, an isophorone-terminated polytetramethylene prepolymer, and combinations thereof; and the second reactive component comprises a polyamine, such as a polyamine prepolymer, a bifunctional polyamine prepolymer, a trifunctional polyetheramine, and combinations thereof, wherein the first reactive component reacts with the second reactive component to form a polyurea-based curable composition; the first reactive component comprises a Michael donor group, such as an amine, a thiol, an enolate, an alcohol, or an enamine, and the second reactive component comprises a Michael acceptor group, wherein the first reactive component reacts with the second reactive component to form a Michael addition-based curable composition; the first reactive component comprises a Michael donor group, such as a prepolymer and / or monomer of an amine-containing compound, such as a polyamine prepolymer, a polyamine monomer, or a blend thereof, and the second reactive component comprises a Michael acceptor group, the first reactive component reacting with the second reactive component to form an aza-Michael addition-based curable composition; the first reactive component comprises a Michael donor group, the Michael donor group comprising a prepolymer and / or monomer of a thiol-containing compound, such as a polythiol prepolymer, a polythiol monomer, or a blend thereof, and the second reactive component comprises a Michael acceptor group, the first reactive component reacting with the second reactive component to form a thia-Michael addition-based curable composition; the first reactive component comprises an epoxy resin, such as a polyepoxide prepolymer, a polyepoxide monomer, or a blend thereof, and the second reactive component comprises a thiol-containing compound, the first reactive component reacting with the second reactive component to form a polysulfide-based curable composition; The first reactive component contains a catalyst and / or an activator, such as an oxidation compound, such as a metal peroxide, a metal oxygen-containing salt, and / or other oxidants or their blends, such as manganese dioxide, and the second reactive component contains a thiol compound, and the first reactive component reacts with the second reactive component to form a polysulfide-based curable composition; The first reactive component contains a thiol, such as a polythiol prepolymer, a polythiol monomer, or their blend, and The second reactive component contains an alkylene-containing compound, and the first reactive component reacts with the second reactive component to form a thiol-ene-based curable composition; The first reactive component contains an epoxy group-containing compound, such as a polyepoxide prepolymer, a polyepoxide monomer, or their blend, and the second reactive component contains an amine compound, and the first reactive component reacts with the second reactive component to form an epoxy-amine-based curable composition; The first reactive component contains an epoxy group-containing compound, such as a polyepoxide prepolymer, a polyepoxide monomer, or their blend, and the second reactive component contains an acid anhydride compound, such as an acid anhydride prepolymer, an acid anhydride monomer, or their blend, and the first reactive component reacts with the second reactive component to form an epoxy-anhydride-based curable composition; The first reactive component contains a hydroxyl group-containing compound, such as a polyol prepolymer, a polyol monomer, or their blend, and the second reactive component contains an isocyanate compound, such as a polyisocyanate prepolymer, an isocyanate monomer, or their blend, and the first reactive component reacts with the second reactive component to form a polyurethane-based curable composition; Or The first reactive component contains an amine compound, and the second reactive component contains an acetate compound, and the first reactive component reacts with the second reactive component to form a curable composition based on a condensation reaction.

17. The article according to any one of the preceding claims, wherein the curable composition is applied as a plurality of layers, wherein the first curable composition contains a first layer and contains a higher amount of a rheological modifier and / or a filler compared to the second curable composition; wherein the first curable composition is applied as the first layer; wherein the second curable composition is applied to the surface of the first curable composition to form a second layer; wherein the first curable composition contains 1 wt.% to 15 wt.%, such as 1.5 wt.% to 10 wt.% or 2 wt.% to 5 wt.% of a rheological modifier and / or a filler, and the second curable composition individually contains 0 wt.% to 3 wt.%, such as 0.5 wt.% to 2.5 wt.% or 0.75 wt.% to 2 wt.% of a rheological modifier and / or a filler, both based on the weight of the respective curable composition; and wherein the amount of the rheological modifier and / or the filler in the first curable composition is greater than the amount of the rheological modifier and / or the filler in the second curable composition.

18. The article according to claim 17, wherein the viscosities of the first curable composition and the second curable composition measured using a Brookfield viscometer (AMETEK, Inc.) with a No. 7 rotor at 50 rpm and 23 °C are from 1 cps to 1,000,000 cps, such as from 250 cps to 500,000 cps, from 300 cps to 100,000 cps, or from 500 cps to 50,000 cps; wherein the viscosity of the uncured first curable composition is greater than the viscosity of the second curable composition.

19. The article according to any one of claims 17 or 18, wherein the pigment component is applied to the surface of the second curable composition.

20. The article according to any one of the preceding claims, wherein the pigment component is applied to at least a part of the surface of the partially uncured curable composition by spraying, rinsing, dipping, electrostatic means, vibratory discharge, screw conveyor, auger, and / or precision application.

21. The article according to any one of the preceding claims, wherein the curable composition is deposited onto a printing surface and / or into a mold, and wherein the pigment component has been applied to the printing surface and / or the mold before depositing the curable composition.

22. The article according to any one of the preceding claims, wherein the curable composition is applied and then immediately the pigment component is applied in a predetermined pattern or shape to at least a part of the surface of the partially uncured curable composition.

23. The article according to any one of the preceding claims, wherein the curable composition is printed in layers by ambient reactive extrusion, wherein one or more layers comprise rigid portions, flexible portions, foamy portions, tactile portions, two or more portions having different densities, conductive portions, thermally conductive portions, electrically conductive portions, different colors, different rheological properties, and / or different materials having different affinities for water and / or solvents.

24. The article according to any one of the preceding claims, wherein the curable composition is deposited on an existing article, such as an article comprising a thermosetting plastic, a thermoplastic, a metal, wood, a composite material, a ceramic, asphalt, or a combination thereof.

25. The article according to any one of the preceding claims, wherein the curable composition comprises a catalyst, an activator, a promoter, a pigment, a rheology modifier, an organic filler, an inorganic filler, a flame retardant filler, a low density filler, a conductive filler, an adhesion promoter, a plasticizer, a leveling additive, an antifoaming agent, a degassing agent, a surfactant, a desiccant, a dispersant, a wetting agent, a light stabilizer, an emulsifier, a chelating agent, a freeze-thaw control agent, a fungicide, a heat stabilizer, a corrosion inhibitor, a dehumidifying agent, a swelling material, a thermally conductive material, an electrical insulating material, a non-thermally conductive material, and / or a non-electrical insulating material.

26. The article according to any one of the preceding claims, wherein when the pigment component is applied, the degree of hardening / curing of the curable composition does not exceed 75%, such as not exceeding 65%, not exceeding 50%, or from 0 to 75%, such as from 0 to 65% or from 0 to 50%, of the curing / hardening potential of the curable composition.

27. A method of making an article according to any one of the preceding claims, the method comprising: forming a three-dimensional article by environmentally reactive extrusion deposition of a curable composition; applying a pigment component comprising a pigment and / or particles to at least a portion of the surface of the article when the curable composition is at least partially uncured; and hardening the curable composition.

28. The method according to claim 27, wherein the article is a three-dimensional article, and the curable composition is applied by depositing the curable composition onto a substrate to form successive portions or layers and then depositing additional portions or layers of the curable composition onto the underlying deposited portions or layers; wherein the layers are successively deposited to build the three-dimensional article, and wherein covalent bonds can form between the layers.

29. The method according to any one of claims 27 or 28, wherein the pigment component is applied by spraying, rinsing, dipping, electrostatic means, vibratory discharge, auger and / or auger drill.

30. The method according to any one of claims 27 to 29, wherein the pigment component is applied using an auger, the auger comprising an auger sleeve in fluid communication with an auger drill, the auger sleeve being adapted to discharge the pigment component via an auger discharge port.

31. An auger, comprising: an auger sleeve adapted to receive a pigment component comprising a pigment and / or particles, in fluid communication with an auger drill, in fluid communication with an auger discharge port, and adapted to convey the pigment component from the auger sleeve to the auger discharge port; an electric motor adapted to rotate the auger drill; and an auger housing surrounding the auger drill.

32. The auger according to claim 31, wherein the auger discharge port is adapted to receive a funnel adapted to direct application of the pigment component.

33. The auger according to any one of claims 31 or 32, wherein the auger drill is 2 cm to 15 cm long, such as 3 cm to 14 cm long or 4 cm to 13 cm long; and / or comprises a plurality of threads extending from the auger shaft to the inner wall of the auger housing; wherein the width of the threads is 0.2 cm to 2.5 cm, such as 0.25 cm to 2 cm or 0.3 cm to 1.5 cm; and wherein the pitch of the threads is 0.5 cm to 4 cm, such as 0.75 cm to 3.5 cm or 1 cm to 3 cm.

34. The auger according to any one of claims 31 to 33, wherein the electric motor rotates the auger drill at 1 rpm to 180 rpm, such as 25 rpm to 150 rpm or 50 rpm to 125 rpm.

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