Patent application title: Embossed Metallic Flakes Process And Product
James P. Rettker (Crown Point, IN, US)
Eckart America Corporation (Painesville, OH, US)
Bharat J. Adhia (Chagrin Falls, OH, US)
ECKART AMERICA CORPORATION
IPC8 Class: AB22F100FI
Class name: Process shaping liquid metal against a forming surface coating mold surface with a treating agent
Publication date: 2013-08-01
Patent application number: 20130192789
A process for preparing embossed fine particulate thin metal flakes
having high levels of brightness and color intensity. The process
comprises forming a release coat on a flexible polymeric carrier film,
embossing the release coat with a diffraction grating pattern that is
monoruled at an angle above 45°, vacuum metalizing the embossed
release surface with a highly reflective metal such as aluminum, and
solubilizing the metalized release coat in a solvent for removing the
metal from the carrier to form embossed metal flakes that replicate the
embossment pattern. The flakes are recovered from the solution containing
the solvent and release coat polymer while avoiding high shear, particle
sizing or other application of energy that would excessively break up the
flakes, so that the D50 particle size of the flakes is maintained at or
above 75 microns. The flakes have application to coatings and printing
inks that produce extremely high brightness characterized as an optically
apparent glitter or sparkle effect in combination with high color
intensity or chromaticity.
1. A process for making embossed fine particulate thin metallic flakes
having brightness and color intensity, comprising providing a release
surface on a carrier, embossing the release surface with a diffraction
grating pattern having an angular ruling pattern greater than 45.degree.,
metalizing the embossed release surface with a thin reflective metal
film, removing the metal film from the release surface to form a solvent
dispersion of embossed metal flakes that have replicated the diffraction
grating pattern, and controlling the particle size of the flakes
contained in the dispersion to maintain the embossed flakes contained
therein at a D50 particle size at or above 75 microns.
2. The process according to claim 1 in which the metal layer is applied to a polymeric release coat which is coated on the carrier and then embossed with the diffraction grating pattern.
3. The process of forming a first coating containing the embossed metal flakes of claim 1 dispersed in a polymeric binder, in which the first coating has a substantially higher chromaticity reading and a substantially higher color intensity reading at 75.degree. and 110.degree. angular measurements when measured on a multi-angle spectrophotometer, when compared with a second coating containing a dispersion of D50, 50 micron size embossed flakes made by a similar process and contained in the same polymeric binder.
4. The process of claim 1 comprising forming a coating containing a polymeric binder containing the embossed metal flakes of claim 1.
5. The process according to claim 1 in which the embossed metal flakes have a diffraction grating pattern of less than about 14,000 grooves per centimeter, a flake thickness from about 50 nm to about 100 nm, and a groove depth of less than about 140 nm.
6. The process according to claim 1 in which the embossed metal flakes have a particle size range of (a) or (b): (a) from 75 to 200 microns, or (b) from 75 to 150 microns.
7. The process according to claim 1 in which the embossed metallic flakes have a thickness range of (a) or (b): (a) from about 5 nm to about 100 nm, or (b) from about 50 nm to about 100 nm; or alternatively, an optical density from about 1.0 to about 3.5.
8. The process according to claim 1 in which the embossed metallic flakes contained in the solvent dispersion are subjected to no applied energy that would reduce particle size greater than low speed mixing, or would reduce particle size more than 20 microns.
21. The process of claim 1, wherein controlling the particle size of the embossed metal flakes contained in the dispersion to maintain the embossed flakes contained therein at a D50 particle size at or above 75 microns comprises, allowing the embossed metal flakes to settle to a bottom of a vessel, removing a resin-rich liquid layer from a top of said vessel, and collecting the embossed metal flakes.
22. The process of claim 1, wherein after removing the metal film from the release surface, said process is free of centrifuging of the solvent dispersion, sonolater treatment of the solvent dispersion, and high shear mixing of the solvent dispersion.
23. The process of claim 1, wherein the embossed metal flakes have a diffraction grating pattern of from about 5,000 to less than about 14,000 grooves per cm.
24. The process of claim 1, wherein the embossed metal flakes have a groove depth to flake thickness ratio of greater than 1.0.
25. The process of claim 1, wherein said angular ruling pattern is 60.degree..
26. The process of claim 1, wherein said embossed metal flakes have an optical density of 3.0 or more and a D50 average flake size greater than 200 microns.
27. The process of claim 1, wherein said embossed metal flakes have a groove depth from about 125 nm to about 140 nm.
FIELD OF THE INVENTION
 This invention relates to a process for producing embossed metal flakes and the use of such of flakes in coatings and printing inks. More particularly, the process involves techniques for producing embossed flakes having high levels of brightness and color intensity when formulated in coatings and printing inks.
 Metallic flakes have been used for many years in decorative coatings to produce different visual effects. Metallic flakes are used in metallic automotive paints, for example. These flakes are typically made by vacuum metalizing the smooth surface of a release coat applied to a flexible temporary carrier film, solubilizing the metalized release surface to remove the metal film from the carrier, and breaking up the metal into flakes.
 In addition to automotive paints, metallic flakes have been used in other coating compositions, paints, enamels, lacquers, and the like, including coatings that produce a highly reflective metalized surface for metallic-like or mirror-like optical effects. In these coatings, small particle size metal flakes below about 50 microns in size can produce good reflectivity along with the opacity necessary to provide complete 100% coverage for the mirror-like effects. Larger flakes which may be reflective are usually more spread out when applied as a coating, and therefore, may not produce the necessary opacity or hiding ability for yielding a highly reflective mirror-like surface.
 The small metal flakes also have tended to be more useful in compositions such as printing inks where the larger flake sizes are not as usable in certain types of printing equipment.
 In another development, metallic flakes have been produced with embossed patterns in the form of diffraction grating or holographic image patterns. These flakes produce certain iridescent effects when used in coatings or printing inks. These flakes have been made by a process described in U.S. Pat. No. 5,672,410 to Miekka et al., assigned to Avery Dennison Corporation. The entire disclosure of the '410 patent is incorporated herein by reference. In the process of making embossed flakes according to the '410 patent, metallic flakes having a controlled particle size below about 50 microns are produced. The metallic flakes can be produced by different embossing techniques followed by metalizing the embossed surface, stripping the metal to form a dispersion of flakes, and then breaking up the metal flakes into smaller size flakes approximately 10 to 50 microns in size. The dispersed metal particles are subjected to high speed mixing or ultrasonic mixing which breaks up the particles into the desired size range without destroying the reflectivity of the flakes. The metallic film obtained by this process resembles the brilliance, reflective gloss and hiding power of commercial metallic foils. Due to the natural orientation of the single layer leafing flake, even when embossed, small amounts of pigment will cover a very large surface area.
SUMMARY OF THE INVENTION
 Briefly, one embodiment of the present invention comprises a process for making embossed fine particulate thin metallic flakes having high levels of brightness and color intensity. The process comprises providing a release surface on a carrier, embossing the release surface with a diffraction grating pattern having an angular ruling pattern greater than 45°, metalizing the embossed release surface with a thin reflective metal film, removing the metal film from the release surface to form a solvent dispersion of embossed metal flakes that have replicated the diffraction grating pattern, and controlling the particle size of the flakes contained in the dispersion to maintain the embossed flakes contained therein at a D50 average particle size at or above 75 microns.
 Another embodiment of the invention comprises reflective metal flakes which have been embossed by replicating a diffraction grating pattern having a monoruled embossing angle above 45°, the particles having a D50 average particle size at or above 75 microns and a flake thickness from about 50 to about 500 angstroms.
 The process of this invention controls the color intensity or chromaticity and brightness of embossed flakes and produces flakes of large particle size with high levels of color intensity and brilliance. The embossed flakes of this invention have application to coatings and printing inks that produce extremely high brightness characterized as an optically apparent glitter or sparkle effect in combination with high color intensity or chromaticity. The embossed flakes also can be used to produce similar optical effects when used in the decorative layers of multi-layer laminates, including those subjected to thermoforming.
BRIEF DESCRIPTION OF THE DRAWINGS
 FIG. 1 is a schematic cross sectional view illustrating an intermediate embossing step in a process according to principles of this invention.
 FIG. 2 is a schematic diagram illustrating diffraction grating embossments formed at a 45° angle.
 FIG. 3 is a schematic diagram illustrating diffraction grating embossments formed at a 60° angle.
 FIG. 4 is a schematic diagram illustrating reflection angles used for measuring color intensity and chromaticity with a multi-angle spectrophotometer.
 Referring to FIG. 1, a temporary carrier film 10 passes into a coater for applying a release coat 12 to at least one side of the carrier film. In a preferred embodiment, both sides of the carrier film are coated with a thin film of the release coat material. FIG. 1 illustrates one embodiment of the invention which includes embossing the release coat to form a pattern of embossments 14 as described below. The embossed carrier is then metalized with a thin reflective metal film as described below.
 The carrier film is preferably a flexible, foldable, heat-resistant polymeric casting film, preferably biaxially oriented PET. The polyester films Mylar or Hostaphan from American Hoechst are examples of the preferred casting films. The preferred carrier film has an extremely smooth casting surface substantially in the absence of adherent fine particulate materials such as filler particles commonly used for roughening the surface to improve slip properties. The carrier film used for this invention preferably has no slip additive. Such polyester film is commercially available in different grades. A PET Hostaphan grade of 3000 or better, based on surface roughness measurements, is useful in this invention.
 The carrier film can be embossed by various techniques, including embossing the release coat applied to the carrier or embossing the metal layer of a metalized carrier film. The above-mentioned '410 patent describes four separate methods which may be used for forming the embossment pattern. The preferred embossing process involves applying a release coat to the carrier and embossing the release coat as follows.
 The release coat material comprises various polymeric materials which can be embossed with accurately formed embossments (described below) and which can be easily solubilized in an organic solvent. Examples of suitable release coat materials include acrylic resins such as PMMA, acrylic copolymers, PVC, and polystyrene. The release coat material is solubilized in a suitable organic solvent and applied to the carrier film by roll coating techniques. The coated carrier is then subjected to heat for drying the release coat to produce an extremely smooth release surface. The preferred thickness of the release coat is produced by applying the release coat at about 0.8 grams per square meter per side of the carrier, or 1.6 grams per square meter total.
 The release surface is embossed with an embossing roll to form the pattern of embossments 14 on the release surface. The embossments are preferably in the form of a diffraction grating pattern formed by embossing closely spaced apart and regularly spaced apart parallel grooves in the release surface. In one embodiment, the diffraction grating is formed by a regular pattern from 5,000 to less than 14,000 groves per centimeter. In another embodiment, the diffraction grating structure is from about 10,000 to about 12,500 grooves per centimeter.
 Prior to embossing, the release coat is allowed to dry or solidify. The embossing step is then carried out by heating the release coat to above its softening temperature and then embossing the diffraction grating pattern in the release surface. The embossing roll preferably forms the embossments in a monoruled pattern--straight parallel grooves identically shaped and uniformly spaced apart in a single embossing path across the release surface. In one embodiment, the groove pattern has a wavy or sinusoidal cross-sectional structure such as that shown in FIG. 4.
 The grating structure from which the flakes of this invention are made can have a groove depth from about 125 nm to about 140 nm, and more preferably, from about 130 nm to about 135 nm.
 The diffraction grating pattern of embossments described in the '410 patent have been produced commercially in the past by monoruling at a 45° angle. FIG. 2 illustrates such a monoruled embossment pattern 16 and the 45° ruling angle defined as a line drawn from the base of the groove tangential to the adjacent top portion of the groove.
 According to the present invention, the embossing roll forms a diffraction grating pattern by monoruling identically shaped and uniformly spaced-apart parallel grooves each having an embossment angle greater than 45°. In one embodiment, the embossment pattern is a monoruled 60° angle diffraction grating pattern 20 as shown in FIG. 3.
 After forming the embossed release surface, the embossed carrier is passed through a vacuum metalizer for vacuum depositing a metal film on the embossed release coating. In one embodiment in which the release coat is coated on both sides of the carrier, both sides are embossed, and the metal film is vacuum deposited on both sides of the carrier. The thickness of the deposited metal monolayer film is from about 50 to 1,000 angstroms (5-100 nm), controlled by the speed of the web and the evaporation rate. Suitable bright metals for deposition include aluminum, chromium, copper, indium, steel, silver, gold, nickel or Nichrome. Aluminum is a presently preferred metal film.
 In one embodiment, a preferred metal thickness range for a single layer metalized aluminum flake product is from about 50 nm to about 100 nm. The desired metal thickness also can be from 1.0 to 3.5 optical density. Optical density is measured on a MacBeth TR 927 densitometer.
 The metal coated embossed carrier is then passed through a metal stripping machine for removing the metal from the carrier to form flakes. Preferably, the metalized carrier is passed around a series of rollers in a tank containing a suitable solvent for solubilizing the release coat. The preferred solvent is acetone. The metal film passes over the rollers and then past a series of doctor blades for removing the metal particles and release coat material from the carrier. The dispersion of flakes and release coat polymer in the solvent is then pumped to a slurry tank. The resultant dispersion in the slurry tank has a percent solids weight from about 2% to about 4% based on the aluminum flakes and residual polymer solids dispersed in the solvent.
 The flakes contained in the resulting slurry have a desired average particle size at or above about 75 microns. These flakes are maintained at a particle size at or above 75 microns by omitting any high energy mixing or particle sizing steps following the metal stripping process. High energy particle sizing such as centrifuging, sonolater treatment or high shear mixing are avoided. Possibly low shear mixing may be suitable in some instances, but with the object of controlling particle size to at or above about 75 microns. High speed mixing, in addition to reducing particle size, can reduce flake brightness. In one embodiment, single layer aluminum flakes produced by this process had an average (D50) particle size above 75 microns. Flakes within a 75 to 200 micron size range can be produced at optical densities within the range of about 1.0 to about 3.5. In one embodiment, the range of desired particle sizes is generally from about 75 to about 150 microns to produce certain optical effects described below. Such particles have been produced within this size range at an optical density of about 2.0 and by following the process steps described above. Larger particle sizes can be produced with thicker flakes, say greater than about 3.5 optical density.
 The present invention also can produce embossed flakes greater than 200 microns in particle size. In one embodiment flakes with a particle size above 200 microns were produced from thicker flakes having an optical density of 3.0 and above.
 Particle size measurements as described herein are made using a Horiba LA 910 instrument.
 Single layer metal flakes having an average D50 particle size greater than 75 microns have been produced using a diffraction grating similar to FIG. 4, to produce flakes having a thickness in the range of 50 nm to 100 nm. In one embodiment, the flake thickness was about 90 nm. These embossed metal flakes have been produced with a diffractive grating pitch of less than 14,000 lines per centimeter. These diffractive flakes, in one embodiment, had a pitch of less than 12,500 lines per centimeter, and in another embodiment, the diffractive pattern was in the range from about 10,900 to less than 12,000 lines per centimeter. These embossed metal flakes had a groove depth of less than about 140 nm, and in one embodiment, groove depth measured from about 130 nm to about 135 nm. These embossed flakes were characterized by a desired groove depth to flake thickness ratio of greater than 1.0.
 The large embossed flakes produced by this invention can be used in various types of coatings to produce certain controlled optical effects. In one embodiment coatings having greater color intensity combined with a glitter or sparkle effect can be produced. Embossed particles at about 100 micron size can just start to be seen by non-magnified visual observation, which reveals the glitter or sparkle effect produced by the visually observable embossments.
 In one embodiment, the embossed flakes embossed at an angle greater than 45°, and 60° in particular, produced greater reflectivity or brilliance and more color intensity in a coating when compared with prior art flakes made with embossing at a 45° angle.
 The glitter or sparkle effect is produced by the larger particles embossed by the techniques of this invention which produce greater reflectivity than the reflectivity produced by the smaller flakes, say about 50 microns average particle size. This comparison is between the larger particles of this invention made by replicating embossments greater than 45°, and in one embodiment, at a 60° angle, when compared with smaller 50 micron flakes made by replicating embossments at a 45° angle. The smaller flakes have lower reflectivity, i.e., are not as mirror-like or are less brilliant. The increased reflectivity of the larger flakes is produced across all colors of the color spectrum.
 Flakes made with embossments at angles greater than 45° can appear substantially brighter than the same size flake made with embossments at 45°. Flakes made with 60° embossments have been observed to have greater brightness in fluorescent light. The flake made with embossments greater than 45° also had visually observable greater color intensity and color shift. The greater area of the replicated embossments available for reflecting incident light is considered to be a reason for the greater brightness and color effects.
 As mentioned, the glitter or sparkle effect is produced in combination with a greater color intensity when compared with the smaller 50 micron flakes; and the greater color intensity combined with the glitter effect has been observed visually from various coatings as well as demonstrated by numerical data produced by color measurements taken by a multi-angle spectrophotometer as shown in the examples below.
 The larger flakes of this invention can be used to produce the described optical effects in various coating compositions such as paints, inks, enamels and print coats. Resinous binders useful with the invention include acrylic and nitrocellulosic resins. One application of the invention comprises a nail polish enamel containing embossed flakes greater than 75 microns, which exhibits a brighter glitter or sparkle effect and greater color intensity or color shift at certain observation angles when compared with a nail polish enamel containing the smaller (50 micron) flakes. This application of the invention has been observed using a nitrocellulose enamel such as that described in International Patent Publication WO 02/03913 to Kirker Enterprises, Inc., incorporated herein by reference. This nail polish enamel was drawndown on a card, dried and observed for its optical effects. The application of the larger particle size embossed flake with the extremely thin angstrom level particle thickness produces the glitter or color shift effects in coatings such as enamels with the embossed flake sizes at 75 microns or more. The individual particles can just be seen by the naked eye at 100 microns sufficient to observe the glitter or rainbow effects of the embossed particles. The ability of these larger embossed flakes to lay down flat in various coatings also enhances the reflected light and color shift effects which are visually observable.
 Other uses of the larger embossed flakes of this invention are in colored printing inks, inks used in silk screen processes, and cosmetic formulations. The larger flakes of this invention can add glitter or sparkle effects to printing inks and dyes.
 In one embodiment, the larger flakes of this invention were found to have good orientation in nitrocellulosic coating compositions which can be useful for printing inks as well as nail polish enamel.
 Another application is for producing certain visual effects in print coats used in various multi-layer laminates. These can include laminates having a thermoformable polymeric substrate base layer, an opaque pigmented base coat or paint coat applied to the substrate, a metallic print coat applied to the pigmented base coat by various printing techniques for producing a decorative print pattern, and an optional outer clear coat that can be a protective weatherable and abrasion-resistant clear coat. The resulting laminate can be thermoformed to form various shapes without degrading the reflective appearance of the metallic print coat.
 The larger metallic flakes also can be used in highly reflective metallic layers contained in similar thermo-formable multi-layer laminates.
 Embossed flakes greater than 75 microns in size were produced according to the previous description. A PET carrier was coated with an acrylic release coat, embossed with a diffraction grating pattern having a 60° monoruled embossment pattern as described previously, metalized with a vapor deposited aluminum film, and stripped to form a metal flake dispersion. Layer thickness for the metalized film in these examples was approximately 2.0 optical density. The flakes were removed directly after stripping for testing. Particle-sizing such as centrifuging or sonic mixing, that would otherwise reduce particle size, were avoided. The act of centrifuging may not reduce particle size, but running through a pump or high speed mixing will reduce the particle size. The embossed particles had a D50 average particle size of about 114 microns. A sample was drawndown on the black side of a leneta card. This sample was compared with a similar sample containing 50 micron flakes made by 45° embossing also drawndown on the black side of a leneta card. The larger flakes were visually observed to display a more pronounced color shift and color intensity than the smaller flakes.
 The following test data were taken from color measurements using an X-Rite MA 58 Multi-Angle SpectroPhotometer. Color values were taken at three angles of measurement, 45°, 75° and 110°, as shown in FIG. 4. The color readings with higher numerical values indicate greater color intensity. Color readings measured color intensity as follows:
 C*=a*(squared)+b*(squared)=a summation of all averages, measuring chromaticity or color intensity
 Large particle size flakes 45°: a* = -6.51 b* = 4.54 C* = 7.94 75°: a* = 21.94 b* = -37.21 C* = 43.20 110°: a* = 5.53 b* = 29.11 C* = 29.63
TABLE-US-00002 Smaller particle size flakes 45°: a* = -15.14 b* = -7.67 C* = 16.97 75°: a* = 19.82 b* = -33.22 C* = 38.68 110°: a* = 5.19 b* = 15.44 C* = 16.29
 These test data showed that the larger flakes had better color intensity, especially at 75° and 110°, than the smaller flakes even though the larger flakes were more spread out with a greater amount of space between particles than the smaller flakes.
 The larger particle size flakes of Example 1 were decanted by letting the flakes settle to the bottom of a vessel and removing the resin-rich liquid layer from the top of the vessel. The clear liquid was at 2.4% resin solids (when measured by drying and reporting weight difference). The decanted sample contained 4.1% solids by weight. The test data showed that the flakes were brighter with more intense color than the sample that was not decanted.
TABLE-US-00003 2.4% solids - no decant 45°: a* = -13.36 b* = -1.03 C* = 13.40 75°: a* = 31.55 b* = -51.69 C* = 60.55 110°: a* = 5.73 b* = 24.64 C* = 25.30
TABLE-US-00004 4.1% solids - decanted 45°: a* = -28.85 b* = 12.59 C* = 31.48 75°: a* = 40.72 b* = -60.63 C* = 73.03 110°: a* = 2.34 b* = 37.20 C* = 37.27
 The larger particle size flakes of Example 1 were added to the 50 micron flakes (10 parts 50 micron flakes to 2 parts 100 micron flakes) contained in a lacquer and drawndown on a leneta card, both sides. These samples were compared with a similar drawdown of the 50 micron flakes of Example 1. The results showed improved color intensity with the addition of the larger flakes.
TABLE-US-00005 50 micron flakes only (black) 45°: a* = -40.29 b* = -1.00 C* = 40.30 75°: a* = 51.38 b* = -80.13 C* = 95.19 110°: a* = 5.33 b* = 43.79 C* = 44.11
TABLE-US-00006 114 micron flakes added (black) 45°: a* = 41.45 b* = -1.52 C* = 41.47 75°: a* = 52.91 b* = -81.40 C* = 97.09 110°: a* = 4.10 b* = 42.71 C* = 42.91
TABLE-US-00007 50 micron flakes only (white) 45°: a* = -38.82 b* = 1.97 C* = 38.87 75°: a* = 42.04 b* = 70.80 C* = 82.34 110°: a* = 5.06 b* = 34.50 C* = 34.87
TABLE-US-00008 114 micron flakes added (white) 45°: a* = 46.17 b* = 2.47 C* = 46.24 75°: a* = 45.06 b* = -73.90 C* = 86.59 110°: a* = 4.91 b* = 34.17 C* = 34.52
Patent applications by James P. Rettker, Crown Point, IN US
Patent applications by ECKART AMERICA CORPORATION
Patent applications in class Coating mold surface with a treating agent
Patent applications in all subclasses Coating mold surface with a treating agent