RETROREFLECTIVE PIGMENTS AND PAINTS
20230126880 · 2023-04-27
Inventors
Cpc classification
C01P2004/61
CHEMISTRY; METALLURGY
C08K2201/006
CHEMISTRY; METALLURGY
C09C1/0015
CHEMISTRY; METALLURGY
C01P2006/60
CHEMISTRY; METALLURGY
C09D7/70
CHEMISTRY; METALLURGY
C08K2201/005
CHEMISTRY; METALLURGY
C09D133/08
CHEMISTRY; METALLURGY
International classification
C09D133/08
CHEMISTRY; METALLURGY
Abstract
Disclosed herein are retroreflective pigments and paints including the retroreflective pigments.
Claims
1. A retroreflective pigment comprising a micrometer-size metal flake having a retroreflective structure.
2. The retroreflective pigment of claim 1, wherein the retroreflective pigment has a surface area in the range of from 100 .Math.m.sup.2 to 60,000 .Math.m.sup.2.
3. The retroreflective pigment of claim 1, is wherein the retroreflective pigment comprises a metal flake having a mean diameter in the range of from 10 .Math.m to 100 .Math.m, and a material thickness in the range of from 20 nm to 1,000 nm, wherein the metal flake includes at least one retroreflective structure.
4. The retroreflective pigment of claim 1, wherein the retroreflective structure is a cube corner structure and the base of the cube corner structure forms an equilateral triangle having a side length in the range of from 2 to 30 .Math.m.
5. The retroreflective pigment of claim 4, wherein the metal flake includes at least two cube corner structures, at least one in a front face of the metal flake, and at least one in a reverse face of the metal flake.
6. The retroreflective pigment of claim 1, wherein the retroreflective pigment is obtained by embossing a thin metal foil.
7. The retroreflective pigment of claim 1, wherein the retroreflective pigment is obtained by physical vapor deposition (PVD) of metal on a preform or on a substrate.
8. The retroreflective pigment of claim 7, wherein the preform is comprised of a heat resistant polymer, and the substrate is comprised of glass.
9. The retroreflective pigment of claim 1, wherein the retroreflective pigment is comprised of aluminum.
10. A paint comprising the retroreflective pigment of claim 1.
11. The paint of claim 10, wherein the concentration of the retroreflective pigment in the paint is in the range of from 0.01 to 10 wt.-%, relative to the total weight of the paint.
12. The paint of claim 10 further comprising non-retroreflective effect pigments.
13. The paint of claim 10 further comprising an acrylic resin.
14. The paint of claim 10 further comprising a polyurethane resin.
15. A coating obtained from the paint of claim 10, wherein the retroreflective pigment is evenly distributed throughout the surface of the coating and the fraction of the surface area of the coating covered by the retroreflective pigment is at least 0.01%, relative to the total surface area of the coating.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
DETAILED DESCRIPTION
[0021] In the present disclosure, the concept of retroreflection is applied to effect pigments. Typically, such effect pigments are dispersed in paints to create special color or gloss effects. Metal flakes are widely used as effect pigments. Light incident on the effect pigments is reflected in nearly specular direction by the (approximately) flat surface of each individual flake.
[0022] In contrast, the flakes used in the present disclosure are three-dimensionally structured with retroreflective geometries. Thus, radiation incident upon the structured area of such flakes is retroreflected to the source and not in the specular direction. One example of a suitable effect pigment is a micrometer-size metal flake with a retroreflective surface structure.
[0023] Retroreflective pigments reflect incoming light in a narrow beam about the direction opposite to the direction of the incoming light. Retroreflection serves to make retroreflective objects much brighter than they would be with ordinary reflection, typically by a factor of 10 to 1000.
[0024] The directly measured value of retroreflectivity is the ratio of the retroreflected luminous intensity I (candela, cd) and the illuminance E (lux, Ix) at the plane of the object. It is called the coefficient of luminous intensity CIL. The unit is candela per lux.
[0025] In one embodiment, the retroreflective pigment of the present disclosure has a CIL value of more than 1 mcd×lx.sup.-1, for instance, more than 10 mcd×lx.sup.-1, or even more than 100 mcd×lx.sup.-1. In one embodiment, the retroreflective pigment of the present disclosure has a CIL value in the range of from 5 to 500 mcd×lx.sup.-1, e.g., 20 to 400 mcd×lx.sup.-1, or 30 to 300 mcd×lx.sup.-1.
[0026] In one embodiment, the retroreflective pigment of the present disclosure is comprised of a metallic material. In a particular embodiment, the retroreflective pigment of the present disclosure is comprised of aluminum. In another particular embodiment, the retroreflective pigment of the present disclosure is comprised of brass or bronze. In still another particular embodiment, the retroreflective pigment of the present disclosure is comprised of copper. In another particular embodiment, the retroreflective pigment of the present disclosure is comprised of silver. In yet another particular embodiment, the retroreflective pigment of the present disclosure is comprised of gold. In still another particular embodiment, the retroreflective pigment of the present disclosure is comprised of tin. In yet another particular embodiment, the retroreflective pigment of the present disclosure is comprised of zinc. In another particular embodiment, the retroreflective pigment of the present disclosure is comprised of lead. In another embodiment, the retroreflective pigment is comprised of a substrate material coated with a thin oxide layer.
[0027] In one embodiment, the retroreflective pigment of the present disclosure retroreflects light with a wavelength in the range of from 850 nm to 950 nm, e.g., 905 nm. In another embodiment, the retroreflective pigment of the present disclosure retroreflects light with a wavelength in the range of from 1500 nm to 1600 nm, e.g., 1550 nm.
[0028] In one embodiment, the retroreflective pigment of the present disclosure has a surface area in the range of from 100 .Math.m.sup.2 to 60,000 .Math.m.sup.2, for instance, 100 .Math.m.sup.2 to 10,000 .Math.m.sup.2. In the context of the present disclosure, the surface area is the area of one face of the substantially planar part of the metal flake. In one embodiment, the retroreflective pigment of the present disclosure has an equivalent diameter in the range of from 10 .Math.m to 100 .Math.m. The equivalent diameter d is obtained from the surface area A of one face of the retroreflective pigment using the formula d= (4A/.sub.π).sup.½.
[0029] In one embodiment, the retroreflective pigment is an elliptical metal flake, for instance, an aluminum flake, with a first main axis having a length in the range of from 20 .Math.m to 100 .Math.m, e.g., 40 .Math.m, and a second main axis having a length in the range of from 10 .Math.m to 70 .Math.m, e.g., 25 .Math.m. In a particular embodiment, the length of the first main axis is 40 .Math.m and the length of the second main axis is 25 .Math.m.
[0030] In another embodiment, the retroreflective pigment is a circular metal flake, e.g., an aluminum flake, with a diameter in the range of from 10 .Math.m to 100 .Math.m, e.g., 20 .Math.m
[0031] In one embodiment, the metal flake has a material thickness in the range of from 20 nm to 1,000 nm, for instance, 200 nm to 300 nm, e.g., 250 nm. The term “material thickness” is used to indicate the thickness of the metal flake perpendicular to its largest surface(s).
[0032] In one embodiment, the retroreflective pigment is a micrometer-size metal flake with at least one retroreflective structure. In one embodiment, the metal flake features at least one retroreflective structure embossed into it. In a further embodiment, the metal flake features at least two retroreflective structures, at least one present in a front face of the metal flake, and at least one present in the reverse face of the metal flake.
[0033] In one embodiment, a cube corner structure is embossed into the center of the metal flake. In one embodiment, the base of the embossed structure forms an equilateral triangle having a side length in the range of from 2 to 30 .Math.m, for instance, 5 to 30 .Math.m, e.g., 17 .Math.m, in the main plane of the flake. The retroreflective structure thus takes the form of a tetrahedron. In another embodiment, two identical cube corner structures are embossed into opposite sides of the metal flake, at a distance to each other. One cube corner structure is embossed into a front face of the metal flake, the other cube corner structure is embossed into a reverse face of the metal flake.
[0034] The retroreflective pigment of the present disclosure combines high surface reflectivity (due to its metallic surface) and directionality of the reflection (due to the retroreflective structure).
[0035] There is no limitation regarding applied geometry if the pigment exhibits (at least nearly) retroreflective properties. For instance, the retroreflective structure may also take the form of a retroreflective ball or bead; or it may combine sections of cube corner structures, in order to reduce dead areas near the corners that reduce the active retroreflective area. For instance, rows or clusters of individual microprisms tilted slightly in different directions can be used to spread the retroreflectivity out over a wider angle of incidence. Further, a rectangular section can be selected from the basic pyramid unit that excludes the dead corners, and an array of these smaller units butted up to each other can be assembled.
[0036] In one embodiment, the retroreflective pigment of the present disclosure is produced by embossing a thin metal foil, e.g., an aluminum foil. In a further embodiment, metal flakes, e.g., aluminum flakes, are embossed. In another embodiment, the retroreflective pigment of the present disclosure is produced by physical vapor deposition (PVD) of metal, e.g., aluminum, on a preform or on a substrate. In the context of the present disclosure, a preform is a support featuring a desired surface structure. In one embodiment, the preform is produced by different embossing techniques, and the embossed surface is subsequently metalized with a thin reflective metal film. To obtain the retroreflective pigment, the metal film is removed from the surface. In one embodiment, the preform is comprised of a heat resistant polymer. In the context of the present disclosure, a heat resistant polymer is a polymer that can withstand a temperature of at least 100° C. without melting or decomposing. Examples of suitable polymers include acrylic resins, acrylic copolymers, PVC, polystyrene, and polyesters, such as PET. In still another embodiment, production of the retroreflective pigment involves formation of a metal film on a glass substrate, e.g., a glass sheet or foil. The substrate does not necessarily need to be a preform. In a further embodiment, the metal film is not removed from the glass substrate.
[0037] The present disclosure also provides a paint comprising the retroreflective pigment of the present disclosure. The paint of the present disclosure can be used in coatings, e.g., industrial coatings, in particular, automotive coatings.
[0038] In one embodiment, the concentration of the retroreflective pigment in the paint is in the range of from 0.01 to 10 wt.-%, relative to the total weight of the paint.
[0039] In a further embodiment, the concentration of the retroreflective pigment in the paint is in the range of from 0.1 to 5 wt.-%, relative to the total weight of the paint, e.g., from 0.5 to 2 wt.-%, for instance, 1 wt.-%.
[0040] In one embodiment, the paint additionally comprises non-retroreflective effect pigments, such as flat metal flakes, iridescent particles, or interference pigments. In a further embodiment, a fraction of the effect pigments present in the paint, i.e., a metallic paint or an iridescent paint, is substituted by the retroreflective pigments of the present disclosure.
[0041] The retroreflective pigments of the present disclosure can be dispersed in combination with other effect pigments. They can even be used in coating layers positioned below layers containing scattering pigments (e.g., in solid coatings).
[0042] In one embodiment, the paint comprises a polyurethane resin. In another embodiment, the paint comprises an acrylic resin. In a further embodiment, the paint comprises a copolymer comprising urethane and acrylic functionalities.
[0043] The present disclosure also provides coatings which are obtained from the paints of the present disclosure. In one embodiment, the coating is an automotive coating. In another embodiment, the coating is a coating on a solid object comprised of, for instance, metal, wood, plastics, ceramics, or glass. In still another embodiment, the coating is a textile coating.
[0044] The retroreflective pigment is evenly distributed throughout the surface of the coating. In one embodiment, the fraction of the surface area of the coating covered by the retroreflective pigment is at least 0.01%, relative to the total surface area of the coating, for instance, at least 1%, or at least 5%. In one embodiment, the fraction of the surface area of the coating covered by the retroreflective pigment is in the range of from 0.01% to 90%, relative to the total surface area of the coating, e.g., from 1% to 70%, or from 3% to 50%, or from 5% to 35%, or even from 25% to 35%.
[0045] In one embodiment, the orientation of the flakes of the retroreflective pigment in the coating of the present disclosure is substantially parallel to the surface of the coating, i.e., the angle between the surface of the coating and the main plane of the flakes is (0°±4°).
[0046] In a particular embodiment, the retroreflective pigment is a micrometer-size metal flake with at least one retroreflective structure. In one embodiment, the metal flake has a mean diameter in the range of from 10 .Math.m to 100 .Math.m, e.g., 20 .Math.m to 70 .Math.m, and a material thickness in the range of from 20 nm to 1,000 nm. In one embodiment, the metal flake features at least one retroreflective structure embossed into it. In a further embodiment, the metal flake features at least two retroreflective structures, at least one present in the front face of the metal flake, and at least one present in the reverse face of the metal flake. In one embodiment, the at least one retroreflective structure is a cube corner structure and the base of the cube corner structure forms an equilateral triangle having a side length in the range of from 2 to 30 .Math.m. In a further embodiment, the metal flake features at least two cube corner structures, at least one in a front face of the metal flake, and at least one in the reverse face of the metal flake.
[0047] In another particular embodiment of the coating, the retroreflective pigment is an elliptical metal flake with a first main axis having a length in the range of from 20 .Math.m to 100 .Math.m, and a second main axis having a length in the range of from 10 .Math.m to 70 .Math.m, and a material thickness in the range of from 20 nm to 1,000 nm, the metal flake featuring at least one retroreflective structure embossed into it, the embossed retroreflective structure being a cube corner structure and the base of the cube corner structure forming an equilateral triangle having a side length in the range of from 2 to 30 .Math.m. In a further embodiment, the metal flake features two of the cube corner structures embossed into opposite faces of the metal flake.
[0048] As already mentioned above, the orientation of the flakes of the retroreflective pigment in the coating is substantially parallel to the surface of the coating. By using pigments comprising flakes having at least one cube corner structure on each of their two faces, it is made sure that at least one of the at least two cube corner structures always has the correct orientation for retroreflecting incident radiation.
[0049] The subject matter of the present disclosure is further described and explained with reference to the accompanying drawings.
DETAILED DESCRIPTION OF THE DRAWINGS
[0050]
[0051]
[0052]
[0053] Standard (thus, flat surface) aluminum flakes are used in
[0054]
[0058] The relative intensity [%] of a reflected Lidar signal is depicted as a function of the angle of Lidar signal incidence [°], relative to the surface normal of the coating. The reflection curve of a Lambertian reference 1 also is shown in the diagram.
[0059] Curves 2, 3, 4 represent the simulated reflectance of a coating comprised of a 20 .Math.m base coat layer on a perfect absorber substrate, covered by a clear coat layer. The base coat comprises 1 wt.-% of pigment, relative to the total weight of the base coat. The pigments are evenly distributed throughout the base coat layer and cover approximately 31% of the total surface area of the coating.
[0060] The reflectance of the Lambertian reference 1 decreases with increasing angle of incidence. The Lambertian reference 1 has an ideal diffusely reflecting surface which obeys Lambert’s cosine law.
[0061] Coating 2 comprising standard aluminum flakes shows high reflectivity at low angles of incidence, due to the specular reflection from the aluminum flakes which are oriented in parallel to the coating surface. As the angle of incidence increases, reflectivity quickly decreases and then drops to nearly zero.
[0062] Coating 3 comprising aluminum flakes having a diffraction grating surface (as described in US 2014/0154520 A1) with periodicity g=1.3 .Math.m shows two local maxima of Lidar reflectivity at approximately 25 to 30° angle of incidence, and approximately 45°, respectively, due to the diffraction of the incident signal (n=-1 and n=-2, respectively).
[0063] Coating 4 comprising retroreflective pigments of the present disclosure (as shown in
[0064]
[0065] Each curve represents the measured reflection of a Lidar signal having a wavelength λ of 905 nm from a multilayer coating on a black plastic substrate. The multilayer coating is comprised of, in sequence, a primer layer, a first 20 .Math.m base coat layer BC1, a second 20 .Math.m base coat layer BC2, and a clear coat layer.
[0066] Curve 1 is the measured reflection curve of a coating comprising 10 wt.-%, relative to the total weight of BC1, of carbon black dispersed in BC1, and 1.43 wt.-%, relative to the total weight of BC2, of aluminum flakes having a diffraction grating surface as described in US 2014/0154520 A1 (Metalure® Prismatic H-50720, ECKART GmbH, 91235 Hartenstein, Germany) dispersed in BC2.
[0067] Curve 2 is the measured reflection curve of a coating comprising 20 wt.-%, relative to the total weight of BC1, of a NIR-transparent black pigment dispersed in BC1, and 1.43 wt.-%, relative to the total weight of BC2, of aluminum flakes having a diffraction grating surface as described in US 2014/0154520 A1 (Metalure® Prismatic H-50720, ECKART GmbH, 91235 Hartenstein, Germany) dispersed in BC2.
[0068] Curve 3 is the measured reflection curve of a coating comprising 10 wt.-%, relative to the total weight of BC1, of carbon black dispersed in BC1, and 1 wt.-%, relative to the total weight of BC2, of standard aluminum flakes (Metalure® A-31017AE, ECKART GmbH, 91235 Hartenstein, Germany) dispersed in BC2.
[0069] Curve 4 is the measured reflection curve of a coating comprising 20 wt.-%, relative to the total weight of BC1, of a NIR-transparent black pigment dispersed in BC1, and 1 wt.-%, relative to the total weight of BC2, of standard aluminum flakes (Metalure® A-31017AE, ECKART GmbH, 91235 Hartenstein, Germany) dispersed in BC2.
[0070] Coatings 1 and 2 comprising aluminum flakes having a diffraction grating surface as described in US 2014/0154520 A1 show high reflectivity at low angles of incidence and an additional local maximum of Lidar reflectivity at approximately 25 to 30° angle of incidence. This local maximum appears when one diffraction order of the Lidar wavelength is directed towards the Lidar source.
[0071] Coatings 3 and 4 comprising standard aluminum flakes show high reflectivity at low angles of incidence, due to the specular reflection from the aluminum flakes which are oriented in parallel to the coating surface. As the angle of incidence increases, reflectivity quickly decreases and then drops to nearly zero.
[0072]
[0073]
[0077]