The present invention relates to opaque glitter particles and in particular to a glitter having metallic appearance.
Glitter is nearly ubiquitous throughout the world and is used to decorate packaging, clothing, the human body, sporting goods, and many other articles. Glitter, which is a plurality of particles having a regular or irregular periphery, is known in forms that include light reflecting or light refracting material. For example, glitter is described in U.S. Pat. Nos. RE 31,780 (Cooper et al.), U.S. Pat. No. 3,764,067 (Coffey et al.), U.S. Pat. No. 4,310,584 (Cooper et al.), and U.S. Pat. Appl. No. 20060228553 (Argoitia et al.); the patents and application are incorporated herein by reference.
Glitter may be clear or may be provided in a variety of colors such as silver, gold, blue, red, etc., or mixtures thereof; and may be provided in a variety of shapes such as circles, squares, rectangles, triangles, diamonds, stars, symbols, alphanumerics (i.e., letters and/or numbers), or mixtures of different shapes.
What is most noticeable about articles coated with glitter is that they tend to glitter or sparkle even when the light source, the coated article and the observer are stationary. Relative movement between the light source, coated article and observer is not required to perceive the glittery appearance of coated articles. Glitter particles each have a large surface area available for reflection, and the glittery effect comes from the misalignment of these particles. However, when relative movement is present, a glitter-coated article tends to sparkle in a dynamic manner wherein the location from where the sparkling effect is viewed, appears to constantly change with movement. Glitter is most noticeable when the glitter particles are opaque; hence, glitter is preferably formed of an opaque reflective material. Non-opaque glitter particles tend to be faint and washed-out in appearance.
Glitter is commercially available in a variety of colors, shapes and sizes. Since the human eye can barely perceive any glittery effect from reflective particles less than 20 microns in diameter, true glitter particles tend to be larger than 50 microns in diameter. For a pleasing visual effect, it is also preferable for glitter particles to be substantially uniform in shape and size. Having some particles that are too large and significantly larger than other adjacent particles lessens the effect that glitter provides, as the eye tends to focus momentarily on the larger particles distracting the viewer. In contrast, if particles are too small, they simply take up valuable space without providing any perceivable glittery effect.
In order for paints and inks to appear truly “glittery,” the particles have to be of a diameter similar to conventional glitter; that is, greater than about 30 microns and preferably more than 50 microns and up to or greater than 2000 microns.
Although the large particles are desirous for use as glitter, such particles tend to curl, losing their ability to serve as high quality glitter which needs to be relatively flat.
In summary, it is preferred to have glitter particles which are substantially flat, uniform in size and shape, and opaque. It is also desirous to have glitter particles which are at least 30 microns in size, and which have high reflectivity.
In the last few years, the demand for highly reflective glitter having metallic appearance grew rapidly, especially for the glitter made of aluminized foil, which has a neutral silver color and creates a sparkling “brilliant” effect due to the high reflectivity of aluminum. Advantageously, this glitter is cost effective and convenient to use in a medium of any color.
Conventionally, the reflective glitter is made of a foil formed by a polymeric film coated with aluminum. The metalized coating is typically vacuum deposited; and the foil is optionally coated with clear lacquer which may be tinted with a dye.
However, in painting applications, the conventional glitter produces a so-called “salt-and-pepper effect,” that is appearance of black specks or smears on the surface of a paint coat. To avoid the salt-and-pepper effect, a layer of glitter-loaded paint is further coated with additional layers of a clear coating material. In some instances, very thick clear layers are necessary to avoid black specs and achieve a smooth glittering surface.
It is likely that the salt-and-pepper effect is caused by curling of glitter particles or mechanical damage to the particles resulting in separation of the aluminum layer from the organic film, or a combination thereof.
Accordingly, it is desirable to provide metallically-colored reflective glitter with improved robustness, which is more stable to mechanical and chemical impact than the conventional glitter, in order to eliminate or decrease the salt-and-pepper effect in paint coatings including the glitter.
Accordingly, the present invention relates to reinforced opaque glitter comprising uniformly shaped and sized particles. Each of the particles comprises: a transparent organic substrate; a reflective core supported by the transparent organic substrate, one or more robustness-improving layers supported by the transparent organic substrate, for providing rigidity to the particle and for substantially preventing it from curling. Optionally, the particles have lacquer layers at a surface of the particle, on one or both planar sides of the particle.
One aspect of the present invention relates to uniformly shaped and sized glitter particles comprising: a transparent organic substrate including PET; an aluminum layer adjacent directly to the transparent organic substrate; a robustness-improving layer, which is an inorganic transparent protective layer having a thickness of at least 20 nm adjacent directly to the aluminum layer; and, optionally, lacquer layers at the surface of the particle.
Another aspect of the present invention provides uniformly shaped and sized glitter particles including: a transparent organic substrate comprising PET; an aluminum layer; a robustness-improving layer which is an adhesion promoting layer adjacent directly to the transparent organic substrate and the aluminum layer, for promoting adhesion therebetween; and, optionally, lacquer layers at the surface of the particle.
Yet another aspect of the present invention provides glitter particles including: a transparent organic substrate comprising PET; an aluminum layer; a first robustness-improving layer, which is an adhesion promoting layer, adjacent directly to the transparent organic substrate and the aluminum layer, for promoting adhesion therebetween; a second robustness-improving layer, which is an inorganic transparent protective layer having a thickness of at least 20 nm, disposed so that the aluminum layer is located between the first and second robustness-improving layers; and, optionally, lacquer layers at the surface of the particle.
Further, the invention provides uniformly shaped and sized opaque glitter particles, wherein each particle includes an organic substrate having first and second sides, a first layered structure on the first side of the substrate and a second layered structure on the second side of the substrate. The first and second structures each includes a reflective core supported by the organic substrate; one or more robustness-improving layers supported by the organic substrate, for providing rigidity to the particle; and, optionally, a lacquer layer at a surface of the particle. The one or more robustness-improving layers include a transparent inorganic protective layer or an adhesion promoting layer, or both.
In accordance with this invention these glitter particles preferably each have a diameter “d” of at least 30 microns, and a thickness “t” of more than 6 microns wherein t<d/2. The organic support layer provides rigidity for preventing or reducing the particles from curling and for allowing precise cutting of the glitter substrate into discreet particle size.
The invention will be described in greater detail with reference to the accompanying drawings which represent preferred embodiments thereof, wherein:
Due to the glitter particle size, special application techniques had to be developed to produce a defect free, smooth clear coat finish with glitter particles underneath. In many cases this caused a variety of challenges to the painter. The application of glitter-containing coating requires many more hours of extra work, materials, patience and a special talent. The challenge is for the particles to be under the clear coat and make the coating smooth, not damage the glitter particles, and still have good adhesion since the particles are so large. To achieve this, the painter applies a base color coat followed by glitter particles in a paint binder, followed by several clear coat layers. However, sanding as is required between coats results in fracturing or cracking of the glitter particles, making pits in a particle or producing micro shattering similar to a broken windshield. In addition, several clear coats would have to be applied in order to create a film build-up to cover the particle so that it could be sanded without damaging the particle while achieving adhesion between layers. The most challenging and frustrating aspect is that the damage to the glitter particles is not seen until the next layer of clear coat is applied. If the glitter particles are damaged, the micro shattering or pits are filled in by the clear coat causing the defects to be exposed by showing optical differences in depth and smoothness which results in a black or white spot depending on depth or size of damage to the glitter particle. When color shifting glitter having PET/Cr/MgF2/Al/MgF2/Cr layers forming particles was made and tested, it was unexpectedly discovered that many of the challenges listed above decreased or were eliminated and, differently from the conventional silver-colored glitter, color shifting glitter causes a lesser salt-and-pepper effect, if any, and a smooth glitter-containing coating is achievable with fewer clear coats and sanding steps.
It is our understanding that the color shifting glitter is more robust than the conventional neutral glitter made from an aluminized foil. In particular, the color shifting glitter has better adhesion between the PET substrate and layers deposited thereon, because adjacent to the PET substrate is the layer of Chromium known for its good adhesion to PET. Further, in the color-shifting glitter particles, both sides of the aluminum layer are better protected from damage, whereas in the conventional glitter one side of the aluminum layer is covered only with a lacquer layer made of a relatively soft organic material. Additionally, relatively thick layers of hard inorganic materials such as MgF2 provide higher rigidity to the particles.
The discovery has been employed to provide metallically colored glitter having improved mechanical properties.
As described above, particles of the conventional glitter consist of a transparent organic film and a metal layer deposited thereon. Typically, two layers of lacquer, clear or including a colorant, are coated on both sides of the metalized film.
The glitter particles of the instant invention include an organic substrate, preferably transparent, and a reflective core supported by the substrate, wherein a first and a second surface the reflective core have a reflectivity in a part of the visible spectrum of at least 50% and preferably higher than 70%. The reflective core may be a single reflector layer, such as shown in
Differently from the conventional glitter particles, the glitter particles of the instant invention include one or more robustness-improving layers supported by the substrate, for providing robustness and rigidity to the particle. The substrate and the robustness-improving layers are transparent, that is having a transparency of at least 70% in a part of the visible spectrum; preferably all the layers on one side of the reflective core have a total transparency of at least 50%. The robustness-improving layers are colorless or may add a hue to the metallic color of the particles.
The high transparency of all the layers other than the reflector core, which preferably is a highly reflective aluminum layer or has aluminum at the surface of the reflective core, provides bright silver-colored glitter.
The glitter of the instant invention is an opaque glitter which has a metallic color, e.g. silver, gold, etc., and is absent of a color-shifting effect, though it may have a hue provided e.g. by a colored lacquer.
In more detail, the glitter particles of the instant invention will be described now with reference to
A glitter particle 10 shown in
By way of example, the substrate 100 comprises poly(ethylene terephthalate) (PET) and is 1 mil thick. Alternatively, it may comprise other organic materials such as polymethacrylate and poly(vinylbutyral). The thickness of the substrate 100 may range from 0.5 mil to 5 mil. Preferably, the substrate 100 is transparent, but may be partially transparent with a transparency of at least 85%.
In this example, the reflector layer 110 is an aluminum layer of 50 nm thick and the inorganic protective layer 200 is a 200 nm thick layer of MgF2. More generally, the reflector layer 110 is a metal layer, preferably having a reflectivity of at least 50% for at some of the wavelengths in the visible spectrum; more preferably, the reflectivity of the reflector layer is higher than 70%. The reflector layer 110 may contain aluminum, copper, silver, titanium, gold, etc., or alloys thereof. The protective layer 200 preferably includes an inorganic brittle glass-like hard material such as SiO2 and has a thickness of at least 20 nm, preferably 50-400 nm, so as to protect the reflective layer from external damage and to provide rigidity to the particles and prevent them from curling.
Other materials suitable for the protective layer 200 are high index dielectric materials including zinc sulfide (ZnS), zinc oxide (ZnO), zirconium oxide (ZrO2), titanium dioxide (TiO2), diamond-like carbon, indium oxide (In2O3), indium-tin-oxide (ITO), tantalum pentoxide (Ta2O5), cerium oxide (CeO2), yttrium oxide (Y2O3), europium oxide (Eu2O3), iron oxides such as (II)diiron(III) oxide (Fe3O4) and ferric oxide (Fe2O3), hafnium nitride (HfN), hafnium carbide (HfC), hafnium oxide (HfO2), lanthanum oxide (La2O3), magnesium oxide (MgO), neodymium oxide (Nd2O3), praseodymium oxide (Pr6O11), samarium oxide (Sm2O3), antimony trioxide (Sb2O3), silicon, silicon monoxide (SiO), selenium trioxide (Se2O3), tin oxide (SnO2), tungsten trioxide (WO3), combinations thereof, and the like. Other suitable high index dielectric materials include mixed oxides such as those described in U.S. Pat. No. 5,989,626 to Coombs et al., the disclosure of which is incorporated by reference herein. When the materials of U.S. Pat. No. 5,989,626 are used as dielectric layers, they are most commonly oxidized to their stoichiometric state such as ZrTiO4. Non-limiting examples of such mixed oxides include zirconium titanium oxide, niobium titanium oxide, combinations thereof, and the like. Additionally, dielectric materials having a “low” index of refraction can be used, such as those with a refractive index of about 1.65 or less. Nonlimiting examples of suitable low refractive index dielectric materials include silicon dioxide (SiO2), aluminum oxide (Al2O3), metal fluorides such as magnesium fluoride (MgF2), aluminum fluoride (AlF3), cerium fluoride (CeF3), lanthanum fluoride (LaF3), sodium aluminum fluorides (e.g., Na3AlF6 or Na5Al3F14), neodymium fluoride (NdF3), samarium fluoride (SmF3), barium fluoride (BaF2), calcium fluoride (CaF2), lithium fluoride (LiF), combinations thereof, or any other low index material having an index of refraction of about 1.65 or less. It should be appreciated that several of the above-listed dielectric materials are typically present in non-stoichiometric forms, often depending upon the specific method used to deposit the dielectric material as a coating layer, and that the above-listed compound names indicate the approximate stoichiometry. For example, silicon monoxide and silicon dioxide have nominal 1:1 and 1:2 silicon to oxygen ratios, respectively, but the actual silicon to oxygen ratio of a particular dielectric coating layer varies somewhat from these nominal values. Such non-stoichiometric dielectric materials are also within the scope of the present invention. Care should be taken to ensure the thickness of the protective layer 200 is not too high so as to impede the transparency of this layer.
The lacquer layers may include clear organic material such as nitrocellulose or acrylic resins, optionally including a dye for providing a colored hue to the glitter.
According to another embodiment of the instant invention, a glitter particle 20 shown in
By way of example, the adhesion promoting layer 300 substantially comprises Chromium or Titanium and has a thickness of no greater than 6 nm, to provide transparency of at least 85%.
Preferably, the thickness of the adhesion promoting layer 300 when it comprises Chromium or Titanium is in the range of 2-4 nm, in order to increase its transparency. Only few monolayers are necessary in the adhesion promoting layer 300 to increase the bond between the substrate 100 and the reflector layer 110.
Alternatively, the adhesion promoting layer 300 substantially comprises SiOx, where x=1 and 2, or MgF2, or parylene, having a thickness, for example, in the range of 30-200 nm.
According to one embodiment of the instant invention, a glitter particle 30 shown in
In the aforedescribed particles 10, 20, and 30, the reflective layer 110 may be replaced with a reflective core 111, as shown in
According to one embodiment of the instant invention, the metallic-colored glitter particles include an adhesion promoting layer deposited directly on an organic substrate and/or include an inorganic protective layer disposed so that a reflector layer is located between the organic substrate and the inorganic protective layer. Both, the adhesion promoting layer and the inorganic protective layer, are preferably transparent, or thin enough to have a transparency of greater than 85%. Both layers are colorless or may add a hue to the metallic color of the particles.
Optionally, the particles shown in
Optionally, the glitter particles 10, 20, 30, and 40, include lacquer layers at the surface thereof, the same way as the conventional neutral glitter. The lacquer layers may be clear layers of nitrocellulose, acrylic resins, etc., optionally including a dye.
Lacquering of both sides of metallized foil prior to cutting it into glitter is a part of the conventional process. The lacquers are polymeric coatings that are often dyed to give the color to the glitter. Lacquer is a polymeric layer optionally with an organic dye. The dyed lacquers are applied to both sides and in the aluminum side to produce the desired coloration. If a lacquer layer is damaged, the colored glitter pigment loses its color properties and becomes more pastel. The aluminum layer side can also be directly attacked and lose its brightness so that the glitter becomes darker and less reflecting.
In one embodiment, an organic substrate has two layered structures coated on both sides of the substrate. The two layered structures may be same or different, and each of them may be one of the layered structures 11, 21, 31, or 41, described above. Each of the layered structures includes: a reflective core supported by the organic substrate, such as the core 111 or the reflector layer 110; one or more robustness-improving layers supported by the organic substrate, for providing rigidity to the particle; and, optionally, a lacquer layer at a surface of the particle such as the lacquer layers 120. The one or more robustness-improving layers include a transparent inorganic protective layer, similar to the protective layer 200, or an adhesion promoting layer, such as the layer 300, or both. Similar to particles 10, 20, 30, and 40, the particles with two layered structures on both sides of the substrate may have additional layers for improving adhesion within the particle, for example, alternating tensile and contractive layers. Advantageously, the substrate and all the layers between two reflector layers are not visible and therefore are not necessarily transparent. By way of example, glitter particles with two layered structures have the following design: an organic substrate comprising PET, two aluminum reflector layers deposited on each side of the substrate, and two SiO2 protective layers deposited on the reflector layers.
The glitter is manufactured by deposition of thin film layers onto an organic substrate web to form a multilayered foil.
The deposition methods are known in the art. By way of example, a roll-to-roll a double deposition system is employed as shown in
After forming the multilayered coating as described above with reference to
Advantageously, this invention does not require using a release coated substrate and does not remove the coating from the web to make pigment (i.e. flakes). Furthermore, the glitter particles in accordance with this invention preferably all have the same dimensions in contrast to a Gaussian distribution of pigment particles in the prior art that are generally centered about 17 microns. In a preferred embodiment the glitter particles are relatively large in comparison that is to say, they are about 50-500 microns across or more.
Applications for this glitter include paints where such glitter effects are desired i.e. on boats, skis, snow boards, personal watercraft. Such glitter particles can also be used in plastics such as hair combs, toys and appliances.
Thus, this invention provides highly reflective glitter having both an excellent glittering properties and improved robustness, which allows to eliminate or at least significantly decrease the salt-and-pepper effect in paint coatings.
The present application claims priority from U.S. Patent Application No. 60/992,507 filed Dec. 5, 2007. The present application is a continuation-in-part of U.S. patent application Ser. No. 11/363,420 filed Feb. 7, 2006, which claims priority from U.S. Patent Application No. 60/668,852 filed Apr. 6, 2005 and U.S. Patent Application No. 60/694,407 filed Jun. 27, 2005. U.S. patent application Ser. No. 11/363,420 is a continuation-in-part of U.S. patent application Ser. No. 11/028,819 filed Jan. 4, 2005, now U.S. Pat. No. 7,300,695, which is a divisional application of U.S. patent application Ser. No. 11/243,111, filed Sep. 13, 2002, now U.S. Pat. No. 6,902,807. All the aforementioned applications are incorporated herein by reference for all purposes.
Number | Date | Country | |
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60992507 | Dec 2007 | US | |
60668852 | Apr 2005 | US | |
60694407 | Jun 2005 | US |
Number | Date | Country | |
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Parent | 10243111 | Sep 2002 | US |
Child | 11028819 | US |
Number | Date | Country | |
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Parent | 11363420 | Feb 2006 | US |
Child | 12329215 | US | |
Parent | 11028819 | Jan 2005 | US |
Child | 11363420 | US |