Retroreflective and LIDAR-detectable plastic products

Abstract

The present invention relates to a three-dimensional plastic article (1) having an exterior surface (A), wherein at least a portion (B) of the exterior surface (A) has retroreflective properties, the three-dimensional plastic article (1) comprising: a polymer selected from thermoplastic polymers and thermoset polymers; spherical glass beads having a median particle size D50 of 1 to 150 μm and a refractive index of 2.0 to 2.8 measured at a wavelength λ of 589 nm, the spherical glass beads not being hemispherically coated with a light-reflective coating; pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof; and one or more additional components, wherein the retroreflective portion (B) of the exterior surface comprises one or more outer retroreflective surface portions (C) where the spherical glass beads do not protrude from the polymer matrix.

Description

Detailed Description of the Invention

[0001] [Field of the Invention] The present invention relates to a three-dimensional plastic product having retroreflective properties and LIDAR-detectability, and a method for producing said three-dimensional plastic product. The present invention further relates to a modified three-dimensional product comprising said three-dimensional plastic product having one or more retroreflective properties and one or more further parts or components attached thereto, a Laser Imaging Detection And Ranging (LIDAR) method for said three-dimensional plastic product or said modified three-dimensional product, a use of the three-dimensional plastic product in the form of pellets or filaments for the production of ready-to-use three-dimensional plastic products, and further uses of said three-dimensional plastic product or said modified three-dimensional product.

[0002] [Background of the invention] Retroreflective effects are used in a variety of applications, such as to improve the visibility of traffic signs, road signs, fabrics, cars, etc. in dark conditions, or simply to improve their appearance. Retroreflection occurs due to the combined effects of refraction of incident light passing through the top surface of, for example, a spherical glass bead, internal reflection from the lower onside surface of the spherical glass bead, and subsequent refraction of light as it exits the top surface of the spherical glass bead and returns in the direction from which it came.

[0003] The present invention relates to three-dimensional plastic articles, such as vehicle parts. Being able to clearly see objects, such as vehicles, at night or in low-light conditions is a challenge. Retroreflectivity could greatly improve the visibility and / or LIDAR-detectability of such objects. Vehicle parts, particularly automobile parts, typically have very smooth surfaces with a glossy or semi-glossy appearance to be aesthetically appealing. Therefore, there is a need to provide three-dimensional plastic articles with smooth surfaces, particularly plastic vehicle parts with retroreflective properties.

[0004] German Patent Application Publication No. 102016001026 discloses a raw material for 3D printing containing a thermoplastic material and reflective or retroreflective glass beads. German Patent Application Publication No. 102016001026 states that retroreflectivity is observed only when the retroreflective glass beads are located on the surface receiving light. If the retroreflective glass beads are covered with a thermoplastic material, their effect is extremely minimized or eliminated. Therefore, retroreflective injection-molded plastic articles are described as uncommon because the retroreflective glass beads are encapsulated by the plastic. German Patent Application Publication No. 102016001026 further describes a thermoplastic mixture containing more than 50 wt.% reflective glass beads in the resulting reflective object after 3D printing, with the reflective glass beads protruding from the surface of the object. The reflective glass beads protruding from the surface of the object were not covered with a thermoplastic material. Only filaments and 3D printed objects with retroreflective glass beads protruding from the surface and without the glass beads being covered with a thermoplastic material exhibited retroreflective properties. Only DE 102016001026 A1 describes the use of retroreflective glass beads with a refractive index of 1.7 to 1.9, which are preferably coated in a hemispherical shape with a metallic coating.

[0005] WO 2005 / 033194 relates to retroreflective polymeric compounds and articles made therefrom. The compounds and articles include a thermoplastic polymer, glass beads, and metal flakes. At least a portion of the glass beads are hemispherically coated with a metallic coating. Example 1 discloses a composition containing 1.76 wt.% carbon black pigment, 16 wt.% aluminum-coated BaTiO3 microspheres (38 μm; Prizmalite Industries), 4 wt.% uncoated BaTiO3 microspheres (8.5 μm; Prizmalite Industries), 77.36 wt.% ASA thermoplastic polymer, and 0.88 wt.% Sparkle Silver aluminum flakes of unknown size (Silberline Mfg. Co.).

[0006] WO 2005 / 033194 describes pure barium titanate as a transparent, crystalline ceramic with a refractive index of 2.40, and BaTiO microbeads as dense, transparent spheres composed primarily of BaTiO but also containing significant concentrations of SiO, BO, and CaO, as well as trace amounts of other metal oxides. Therefore, BaTiO microbeads do not have a refractive index of 2.40. Prizmalite Industries only offers BaTiO microbeads with a refractive index of 1.9 that are hemispherically coated with an aluminum coating (product P2453BTA). Guidelines for using Prizmalite® P2453BTA retroreflective spheres distributed by Cospheric LLC state that "an aluminum coating on one half of the barium titanate sphere provides the retroreflectivity mechanism. Light passes through the clear half of the sphere and 'reflects' off the aluminum coating. The combination of the 1.9 RI of barium titanate and the aluminum hemispherical coating creates retroreflectivity, resulting in a more intense and direct refraction of light." These guidelines further state, "These coatings are designed to facilitate the migration of microspheres to the surface of the ink or coating in which they are incorporated. The concept of retroreflection relies on the passage of light through the clear, uncoated hemisphere of a glass sphere. Retroreflection cannot occur unless the sphere is physically positioned to allow light to pass through it. Prismalite's coating creates tension between the coating and its surrounding resin that causes the sphere to 'jump' to the surface, thus maximizing its possible exposure to light. Coating the spheres enhances the retroreflective effect by achieving this positioning, and also reduces the amount of spheres needed, as coated spheres work much more efficiently than uncoated ones."

[0007] The inventors have found that the use of spherical glass beads with a refractive index of 1.9 or less does not provide a three-dimensional plastic article with sufficient retroreflective properties, even when combined with pigment flakes, in plastic articles where the spherical glass beads do not protrude from the plastic or polymer matrix.

[0008] As shown in the Experimental section, we found that using a hemispherical aluminum coating on spherical glass beads with a refractive index of 1.9 resulted in poor retroreflective properties in plastic products where the spherical glass beads did not protrude from the plastic or polymer matrix.

[0009] One object of the present invention is to provide a three-dimensional plastic article with improved retroreflective properties and / or improved LIDAR-detectability.

[0010] It is a further object of the present invention to provide a three-dimensional plastic article with improved retroreflective properties and / or improved LIDAR-detectability, wherein the three-dimensional plastic article comprises retroreflective spherical glass beads that do not protrude from the plastic matrix.

[0011] Another object of the present invention is to provide a three-dimensional plastic article having a smooth, glossy or semi-glossy retroreflective surface and / or a smooth, glossy or semi-glossy LIDAR-detectable surface.

[0012] [Summary of the Invention] The inventors have unexpectedly determined that the above objectives can be achieved by using higher refractive index spherical glass beads in combination with pigment flakes in a weight percentage within a continuous plastic matrix. The inventors have further found that providing a hemispherical light-reflective coating on the spherical glass beads adversely affects the retroreflection / LIDAR-detectability of three-dimensional plastic articles in which the spherical glass beads do not protrude from the plastic matrix.

[0013] Thus, in a first aspect, the present invention provides a three-dimensional plastic product (1) having an outer surface (A), at least a portion (B) of the outer surface (A) having retroreflective properties, said three-dimensional plastic product (1) comprising, based on the total weight of the three-dimensional plastic product (1): 25 to 95.9 wt. % of a polymer selected from thermoplastic polymers and thermosetting polymers; 4 to 70 wt.% spherical glass beads, having a median particle size D50 of 1 to 150 μm as measured by laser diffraction and a refractive index of 2.0 to 2.8 as measured at a wavelength λ of 589 nm, wherein the spherical glass beads are not hemispherically coated with a light-reflective coating; 0.1 to 15 wt. % of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or a combination thereof, having a median diameter of 1 to 75 μm as measured by laser diffraction, and 0 to 15 wt.% of one or more further components, The smallest dimension in all directions of the three-dimensional plastic product (1) is at least 500 μm; The retroreflective portion (B) of the outer surface (A) includes one or more outer retroreflective surface portions (C) in which spherical glass beads do not protrude from the polymer matrix; A three-dimensional plastic product (1) is provided.

[0014] In a second aspect, one or more three-dimensional plastic products (1) according to the first aspect and one or more further parts or components (3) attached thereto, or one or more further parts or components (3) and one or more three-dimensional plastic products (1) according to the first aspect attached thereto; Provided is a modified three-dimensional product (2) comprising: a three-dimensional plastic product (1) according to the first aspect, wherein at least a portion of one or more outer retroreflective surface portions (C) of the three-dimensional plastic product (1) according to the first aspect is not covered with one or more further parts or components (3).

[0015] In a third aspect, the present invention provides a method for producing a three-dimensional plastic article (1) with retroreflective properties according to the first aspect, wherein the polymer is a thermoplastic polymer, comprising: (a) providing a thermoplastic polymer, spherical glass beads, pigment flakes, and optional additional ingredients; (b) blending the components provided in step (a) at a temperature above the melting point of the thermoplastic polymer; (c) feeding the mixture obtained in step (b) into a die or extruding the mixture obtained in step (b); (d) cooling the mixture in the mold to a temperature below the melting point of the thermoplastic polymer and removing the three-dimensional plastic article (1) with retroreflective properties from the mold, or cooling the extrudate to a temperature below the melting point of the thermoplastic polymer to provide a three-dimensional plastic article (1) with retroreflective properties. The present invention provides a method comprising:

[0016] In a fourth aspect, the present invention provides a method for producing a three-dimensional plastic product (1) with retroreflective properties according to the first aspect, wherein the polymer is a thermoset polymer, comprising: (a) providing a thermosettable resin, spherical glass beads, pigment flakes, and optional additional ingredients; (b) mixing the ingredients provided in step (a); (c) feeding the mixture obtained in step (b) into a mold; (d) curing the mixture in the mold to provide a three-dimensional plastic article (1) with retroreflective properties; (e) removing the three-dimensional plastic product (1) with retroreflective properties from the mold; The present invention provides a method comprising:

[0017] In a fifth aspect, the present invention provides a method for laser imaging detection and ranging (LIDAR) of a three-dimensional plastic product (1) according to the first aspect or a modified three-dimensional product (2) according to the second aspect, comprising: (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver and optionally a Global Positioning System (GPS); (ii) transmitting electromagnetic radiation from an electromagnetic radiation source of a LIDAR device to the three-dimensional plastic product (1) or the modified three-dimensional product (2); (iii) scanning the electromagnetic radiation reflected by the three-dimensional plastic product (1) or the modified three-dimensional product (2) with a receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation, preferably as a function of time; the distance between the three-dimensional plastic product (1) or the modified three-dimensional product (2) and the LIDAR device; Acceleration of the three-dimensional plastic product (1) or the modified three-dimensional product (2), Deceleration of the three-dimensional plastic product (1) or modified three-dimensional product (2), The direction of movement of the three-dimensional plastic product (1) or the modified three-dimensional product (2), the velocity of the three-dimensional plastic product (1) or the modified three-dimensional product (2), preferably relative to the velocity of the LIDAR device, and 3D images of three-dimensional plastic products (1) or modified three-dimensional products (2) and computing one or more of: The present invention provides a method comprising:

[0018] In a sixth aspect, the present invention provides the use of a three-dimensional plastic product (1) according to the first aspect in the form of filaments or pellets, in which the polymer is a thermoplastic polymer, in the production of a ready-to-use three-dimensional plastic product (1) according to the first aspect, in which the polymer is a thermoplastic polymer.

[0019] In a seventh aspect, the present invention relates to a three-dimensional plastic product (1) according to the first aspect or a modified three-dimensional product (2) according to the second aspect, in laser imaging detection and ranging (LIDAR) of said three-dimensional plastic product (1) or modified three-dimensional product (2), and / or to improve the visibility of the three-dimensional plastic product (1) or the modified three-dimensional product (2) under visible light conditions, and / or for preparing a three-dimensional image of the three-dimensional plastic product (1) or the modified three-dimensional product (2), Provide use.

[0020] definition As used herein, the expression "spherical glass does not protrude from the polymer matrix" means that the spherical glass beads are covered by the polymer matrix. The outer retroreflective surface portion(s) (C) of the three-dimensional plastic product (1) defined herein can have a smooth surface, a glossy appearance, or a semi-glossy appearance where the spherical glass beads are completely embedded in the polymer matrix, but can also have a rougher surface or a matte appearance where the spherical glass beads protrude from the surface but are still covered by the polymer matrix. The terms "plastic" and "polymer matrix" are used interchangeably.

[0021] As used herein, the term "pigment" refers to a colorant in particulate form, such as spheres or flakes, that is insoluble in the binder or solvent used.

[0022] As used herein, the term "dye" refers to a colorant that is molecularly soluble in the binder or solvent used.

[0023] As used herein, the term "colorant" includes pigments as well as dyes.

[0024] As used herein, the term "titanium suboxide" refers to titanium oxide of the formula Ti n O 2n-1 (wherein n is an integer greater than 1) refers to a titanium oxide compound of the formula:

[0025] The term "LIDAR" is an acronym for "light detection and ranging" or "laser imaging, detection, and ranging" and refers to a method of targeting an object with electromagnetic radiation, typically laser light, and determining the range (variable distance) of the object, its velocity, and a 3D representation of the object by measuring the time it takes for the reflected radiation to return to a receiver.

[0026] The term "vehicle" as used herein refers to a physical object suitable for use in transporting people or goods. Non-limiting examples of vehicles in the context of this invention are selected from the group consisting of cars, lorries, trucks, bikes, mopeds, scooters, motorcycles, trains, trams, boats, ships, drones, skateboards, missiles, helicopters, and aircraft. In preferred embodiments, the vehicle is selected from cars, lorries, trucks, bikes, mopeds, scooters, and motorcycles. [Brief explanation of the drawings]

[0027] [Figure 1]

[0023] Figure 1 illustrates what is meant by "interrupted or uninterrupted outer retroreflective surface portions (C)." The figure depicts a three-dimensional plastic product (1) having an outer surface (A), a portion (B) of which has retroreflective properties, and portion (B) including two "uninterrupted" outer retroreflective surface portions (C). [Figure 2A]

[0023] Figure 1 illustrates what is meant by "interrupted or uninterrupted outer retroreflective surface portions (C)." It depicts a three-dimensional plastic product (1) having an outer surface (A), a portion (B) of which has retroreflective properties, and portion (B) containing two "interrupted" outer retroreflective surface portions (C). Both outer retroreflective surface portions (C) are interrupted by portions (B) of the outer surface. [Figure 2B]

[0023] Figure 1 illustrates what is meant by "interrupted or uninterrupted outer retroreflective surface portions (C)." The figure depicts a three-dimensional plastic article (1) having an outer surface (A), a portion (B) of the outer surface (A) having retroreflective properties, and portion (B) including two outer retroreflective surface portions (C), one outer retroreflective surface portion (C) being "interrupted" by outer surface portion (B) and one outer retroreflective surface portion (C) being "uninterrupted." [Figure 3] 1 depicts a three-dimensional plastic article (1) according to the present invention and a modified three-dimensional article (2) comprising a further component (3) attached thereto. The three-dimensional plastic article (1) has an exterior surface (A), a portion (B) of which has retroreflective properties, and portion (B) includes one outer retroreflective surface portion (C) in which spherical glass beads do not protrude from the polymer matrix, surface portion (C) coinciding with portion (B). The outer retroreflective surface portion (C) is not covered by the further component (3) attached to the three-dimensional plastic article (1). [Figure 4] 1 depicts a three-dimensional plastic article (1) according to the present invention and a modified three-dimensional article (2) comprising a further component (3) attached thereto. The three-dimensional plastic article (1) has an outer surface (A), a portion (B) of which has retroreflective properties, and portion (B) comprises two outer retroreflective surface portions (C) in which spherical glass beads do not protrude from the polymer matrix. The two outer retroreflective surface portions (C) are not covered by the further component (3) attached to the three-dimensional plastic article (1). [Figure 5] FIG. 1 depicts a cross-section (perpendicular to the outer retroreflective surface portion (C)) of a three-dimensional plastic article (1) having a smooth, glossy, or semi-glossy outer retroreflective surface portion (C) in which spherical glass beads (4) are completely embedded in a polymer matrix (5). The outer retroreflective surface portion (C) is coincident with the outer surface portion (B). [Figure 6]1 depicts a cross-section of a three-dimensional plastic article (1) with a matte appearance of an outer retroreflective surface portion (C) that is still covered by a polymer matrix (5) with spherical glass beads (4) protruding from the surface to create some roughness, and that is coincident with the outer surface portion (B). [Figure 7] FIG. 1 depicts the retroreflection of the surface of a three-dimensional plastic product under a 45° angle.

[0028] [Detailed explanation] Three-dimensional plastic products The first aspect of the present invention is a three-dimensional plastic product (1) having an outer surface (A), at least a portion (B) of the outer surface (A) having retroreflective properties, and the three-dimensional plastic product (1) is 25 to 95.9 wt. % of a polymer selected from thermoplastic polymers and thermosetting polymers; 4 to 70 wt. % spherical glass beads having a median particle size D50 of 1 to 150 μm as measured by laser diffraction and a refractive index of 2.0 to 2.8 as measured at a wavelength λ of 589 nm, wherein the spherical glass beads are not coated with a light-reflective coating; 0.1 to 15 wt. % of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or a combination thereof, the pigment flakes having a median diameter of 1 to 75 μm as measured by laser diffraction; and 0-15 wt.% of one or more further ingredients It consists of The smallest dimension in all directions of the three-dimensional plastic product (1) is at least 500 μm; The outer retroreflective portion (B) includes one or more outer retroreflective surface portions (C) in which spherical glass beads do not protrude from the polymer matrix; Three-dimensional plastic products (1).

[0029] As will be understood by those skilled in the art, the expression "the three-dimensional plastic product (1) consists of" means that the combined amount of polymer (thermoplastic or thermoset), spherical glass beads, pigment flakes and further components amounts to 100 wt.% of the three-dimensional plastic product (1).

[0030] As used herein, the phrase "exterior surface having retroreflective properties" refers to a surface that, based solely on its composition, is capable of reflecting light impinging on it back in the direction from which it came, regardless of whether the light can actually reach the exterior surface.

[0031] In a preferred embodiment, one or more outer retroreflective surface portions (C) of the three-dimensional plastic article (1) defined herein have a smooth or glossy or semi-glossy appearance, and the spherical glass beads are completely embedded in the polymer matrix. Such a three-dimensional plastic article (1) can be produced in a smooth mold. Such an embodiment is depicted in FIG. 5. In another embodiment, one or more outer retroreflective surface portions (C) of the three-dimensional plastic article (1) defined herein have a rough or matte appearance, and the spherical glass beads protrude from the surface but are still covered by the polymer matrix. Such a three-dimensional plastic article (1) can be produced in a mold with surface roughness. Such an embodiment is depicted in FIG. 6.

[0032] In a preferred embodiment, the surface area of ​​one or more outer retroreflective surface portions (C) of the three-dimensional plastic article (1) defined herein is uninterrupted, meaning that they do not surround an outer retroreflective surface portion (B). Such a preferred embodiment is depicted in Figure 1. In one embodiment, the surface area of ​​one or more outer retroreflective surface portions (C) of the three-dimensional plastic article (1) defined herein is interrupted, meaning that they surround an outer retroreflective surface portion (B) and / or outer surface portion (A). Such an embodiment is depicted in Figure 2a.

[0033] As explained above, a portion (B) of the exterior surface (A) has retroreflective properties. Unlike one or more outer retroreflective surface portions (C), the remaining outer retroreflective surface portion (B) may have spherical glass beads protruding from the surface without being covered by a polymer matrix.

[0034] Unlike Prismalite hemispherically aluminum (HAC) coated barium titanate spherical glass beads having a refractive index of 1.9, spherical glass beads not hemispherically coated with a metal coating and having a refractive index of 2.0-2.8 measured at a wavelength λ of 589 nm do not migrate to the surface of the plastic product during production. Therefore, in a preferred embodiment, the spherical glass beads are uniformly distributed throughout the three-dimensional plastic product (1). In another preferred embodiment, the spherical glass beads and pigment flakes are uniformly distributed throughout the three-dimensional plastic product (1).

[0035] Because the density of typical thermoplastic and thermosetting polymers is much lower than that of spherical glass beads, which have a refractive index of 2.0 to 2.8 measured at a wavelength λ of 589 nm, the volume fraction of the spherical glass beads in the three-dimensional plastic article (1) is typically lower than the volume fraction of the polymer phase, meaning that the spherical glass beads are typically completely encased in a continuous matrix of the polymer phase.

[0036] In preferred embodiments, the surface area of ​​at least the portion (B) of the outer surface (A) having retroreflective properties constitutes at least 1%, more preferably at least 5%, even more preferably at least 10%, such as at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 99% of the surface area of ​​the outer surface (A).

[0037] In a highly preferred embodiment, the surface area of ​​at least the portion (B) of the outer surface (A) having retroreflective properties constitutes 100% of the surface area of ​​the outer surface (A).

[0038] In another preferred embodiment, the surface area of ​​at least a portion (B) of the outer surface (A) having retroreflective properties constitutes 1 to 100% of the surface area of ​​the outer surface (A), more preferably 5 to 100%, even more preferably 10 to 100%, for example 20 to 100%, 30 to 100%, 40 to 100%, 50 to 100%, 60 to 100%, 70 to 100%, 80 to 100%, 90 to 100%, or 95 to 100%.

[0039] In another embodiment, the surface area of ​​at least the portion (B) of the outer surface (A) having retroreflective properties constitutes 1 to 95%, for example 5 to 90%, 10 to 85%, 15 to 80%, or 20 to 75% of the surface area of ​​the outer surface (A).

[0040] In preferred embodiments, the surface area of ​​one or more outer retroreflective surface portions (C) constitutes at least 1%, more preferably at least 5%, even more preferably at least 10%, such as at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 99% of the surface area of ​​portion (B) of outer surface (A).

[0041] In a highly preferred embodiment, the surface area of ​​one or more outer retroreflective surface portions (C) comprises 100% of the surface area of ​​portion (B) of outer surface (A). Such a highly preferred embodiment is depicted in FIG.

[0042] In another preferred embodiment, the surface area of ​​one or more outer retroreflective surface portions (C) constitutes 1 to 100% of the surface area of ​​portion (B) of outer surface (A), more preferably 5 to 100%, even more preferably 10 to 100%, for example 20 to 100%, 30 to 100%, 40 to 100%, 50 to 100%, 60 to 100%, 70 to 100%, 80 to 100%, 90 to 100% or 95 to 100%.

[0043] In another embodiment, the surface area of ​​one or more outer retroreflective surface portions (C) constitutes 1 to 95%, for example 5 to 90%, 10 to 85%, 15 to 80%, or 20 to 75% of the surface area of ​​portion (B) of outer surface (A).

[0044] As will be understood by those skilled in the art, if the surface area of ​​one or more outer retroreflective surface portions (C) constitutes 100% of the surface area of ​​portion (B) of outer surface (A), then the entire surface area of ​​portion (B) of outer surface (A) is constituted by one or more outer retroreflective surface portions (C), i.e., outer retroreflective surface portion (B) and one or more outer retroreflective surface portions (C) coincide.

[0045] In preferred embodiments, the surface area of ​​the one or more outer retroreflective surface portions (C) constitutes at least 1%, more preferably at least 5%, even more preferably at least 10%, such as at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 99% of the surface area of ​​the outer surface (A).

[0046] In a highly preferred embodiment, the surface area of ​​the outer retroreflective surface portion(s) (C) comprises 100% of the surface area of ​​the outer surface (A).

[0047] As will be appreciated by those skilled in the art, if the surface area of ​​one or more outer retroreflective surface portions (C) constitutes 100% of the surface area of ​​outer surface (A), then the entire surface (A) is a single, uninterrupted outer retroreflective surface where no spherical glass beads protrude from the polymer matrix. In this particular case, outer surface (A) coincides with outer retroreflective surface (B), which in turn coincides with outer retroreflective surface portion(s) (C).

[0048] In another preferred embodiment, the surface area of ​​the one or more outer retroreflective surface portions (C) constitutes 1 to 100% of the surface area of ​​the outer surface (A), more preferably 5 to 100%, even more preferably 10 to 100%, for example 20 to 100%, 30 to 100%, 40 to 100%, 50 to 100%, 60 to 100%, 70 to 100%, 80 to 100%, 90 to 100% or 95 to 100%.

[0049] In another embodiment, the surface area of ​​one or more outer retroreflective surface portions (C) constitutes 1 to 95%, for example 5 to 90%, 10 to 85%, 15 to 80%, or 20 to 75% of the surface area of ​​the outer surface (A).

[0050] The three-dimensional plastic article (1) is comprised of the composition defined hereinabove. Thus, the fact that the three-dimensional plastic article (1) has an exterior surface (A) and that at least a portion (B) of the exterior surface (A) has retroreflective properties is a direct result of this particular composition and not a result of a component (3), such as a retroreflective coating, that may be applied to a portion or portions of the three-dimensional plastic article (1) to provide a "modified three-dimensional article (2)."

[0051] No matter how complex the three-dimensional shape of the plastic product (1) is, as long as light can reach the outer retroreflective surface, at least a portion (B) of the outer surface (A) will exhibit retroreflection.

[0052] The three-dimensional plastic product (1) has a minimum dimension in all directions of at least 500 μm. As used herein, the term "minimum dimension in all directions" means that the length, width, and height of the three-dimensional plastic product (1) are at least 500 μm. Thus, the three-dimensional plastic product (1) can be distinguished from, for example, a coating layer, which typically has a thickness much smaller than 500 μm.

[0053] In a preferred embodiment, the three-dimensional plastic product (1) has a smallest dimension in all directions of at least 1 mm, at least 2 mm, at least 3 mm, at least 4 mm, at least 5 mm, at least 6 mm, at least 8 mm or at least 10 mm.

[0054] In another preferred embodiment, the three-dimensional plastic product (1) has dimensions of 500 μm to 10 m, 2 mm to 10 m, 3 mm to 10 m, 4 mm to 10 m, 5 mm to 10 m, 6 mm to 10 m, 8 mm to 10 m or 10 mm to 10 m in all directions.

[0055] In yet another preferred embodiment, the three-dimensional plastic product (1) has a size in all directions of 500 μm to 9 m, 500 μm to 7 m, 500 μm to 5 m, 500 μm to 3 m, 500 μm to 2 m, 500 μm to 1 m, 500 μm to 80 cm or 500 μm to 60 cm.

[0056] In yet another preferred embodiment, the three-dimensional plastic product (1) has dimensions in all directions of 1 mm to 5 m, 2 mm to 3 m, 3 mm to 2 m, 5 mm to 1.8 m, 1 cm to 1.5 m or 2 cm to 1 m.

[0057] In one embodiment, the three-dimensional plastic article (1), in which the polymer is a thermoplastic polymer, has the form of filaments or pellets, which can be used to produce the ready-to-use three-dimensional plastic article (1) according to the first aspect, for example using extrusion and injection molding.

[0058] In another embodiment, where the polymer is a thermoplastic or thermoset polymer, the three-dimensional plastic product (1) is a ready-to-use product, preferably a vehicle part, more preferably a body part, such as a body part selected from the group consisting of a bumper, a mirror housing, a handle, and a radio antenna.

[0059] polymer The three-dimensional plastic article (1) comprises 25 to 95.9 wt. % of a polymer selected from thermoplastic polymers and thermoset polymers, based on the weight of the plastic article (1). As used herein, the terms "thermoplastic polymer" and "thermoset polymer" have their common meanings in the art.

[0060] In one embodiment, the three-dimensional plastic article (1) comprises 25 to 94 wt.%, for example 25 to 92 wt.%, 25 to 90 wt.%, 25 to 85 wt.%, 25 to 80 wt.%, 25 to 75 wt.%, 25 to 70 wt.%, 25 to 65 wt.%, 25 to 60 wt.%, 25 to 55 wt.%, or 25 to 50 wt.% polymer based on the weight of the plastic article (1).

[0061] In another embodiment, the three-dimensional plastic article (1) comprises 27 to 95.9 wt.%, for example 30 to 95.9 wt.%, 35 to 95.9 wt.%, 40 to 95.9 wt.%, 45 to 95.9 wt.%, 50 to 95.9 wt.%, or 55 to 95.9 wt.% polymer based on the weight of the plastic article (1).

[0062] In one embodiment, the polymer is a thermoset polymer, preferably a thermoset polymer selected from the group consisting of phenol formaldehyde (PF), urea formaldehyde (UF), melamine formaldehyde (MF), epoxy (EP), polyurethane (PU), and unsaturated polyester (UP).

[0063] In a preferred embodiment, the polymer is a thermoplastic polymer, more preferably a thermoplastic polymer selected from the group consisting of polyethylene homopolymers and copolymers (PE, LDPE, HDPE, LLDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide (PA), polyoxymethylene (POM), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polysulfone (PSU), polyimide (PI), polybutene (PB), polyether ether ketone (PEEK), poly(acrylonitrile butadiene styrene) (ABS), poly(acrylonitrile butadiene acrylate) (ABA), poly(acrylic styrene acrylonitrile) (ASA), polylactic acid (PLA), nylon, and blends thereof.

[0064] In an even more preferred embodiment, the polymer is a thermoplastic polymer selected from the group consisting of polyethylene (PE, LDPE, HDPE, LLDPE), polypropylene (PP), polystyrene (PS) and polyethylene terephthalate glycol (PETG).

[0065] spherical glass beads As defined hereinabove, the three-dimensional plastic product (1) comprises spherical glass beads, the spherical glass beads having a median particle size D50 of 1 to 150 μm as measured by laser diffraction, and a refractive index of 2.0 to 2.8 as measured at a wavelength λ of 589 nm, and the spherical glass beads are not hemispherically coated with a light-reflective coating.

[0066] In a preferred embodiment, the term "glass" in "spherical glass beads," as used herein, refers to a non-crystalline, amorphous, solid, transparent material made of oxides. In another embodiment, the term "glass" in "spherical glass beads" refers to a solid, transparent material made of oxides and containing some microcrystallinity. The refractive index of spherical glass beads is closely related to the density of glass, but the relationship is not linear. Due to the nature of glass, density is approximately an additive function of its composition. The density of spherical glass beads with a refractive index of 1.5 to 2.8 is typically 2.5 to 4.5 g / cm. 3 It changes with.

[0067] In a preferred embodiment, the spherical glass beads have a refractive index of 2.0 to 2.6, preferably 2.1 to 2.4, measured at a wavelength λ of 589 nm.

[0068] In another embodiment, the spherical glass beads as defined herein comprise at least two types of spherical glass beads.

[0069] Oxides that can be used in the glass are oxides of silicon, boron, aluminum, sodium, barium, vanadium, titanium, lanthanum, strontium, zirconium, potassium, magnesium, iron, calcium, zinc, lithium, barium, and lead. Spherical glass beads can contain various combinations of, for example, silica (SiO), boron oxide (BO), phosphorus pentoxide (PO), vanadium pentoxide (VO), arsenic trioxide (AsO), germanium oxide (GeO), calcium oxide (CaO), sodium oxide (NaO), magnesium oxide (MgO), zinc oxide (ZnO), aluminum oxide (AlO), potassium oxide (KO), iron oxide (FeO), lead oxide (PbO), barium oxide (BaO), barium titanate (BaTiO), titanium oxide (TiO), lithium oxide (LiO), strontium oxide (SrO), lanthanum oxide (LaO), and zirconium oxide (ZrO). Silica and boron oxide generally have the lowest densities. Therefore, glasses containing large weight percentages of these oxides generally produce glass beads with low refractive indices. The refractive index can be increased by adding higher molecular weight oxides. Preferably, the spherical glass beads do not contain PbO.

[0070] Glass beads having a refractive index in the range of 1.5 to 2.51 and their compositions with respect to oxides are disclosed in WO 2014 / 109564, which is incorporated herein by reference in its entirety. Transparent glass beads having a refractive index greater than 2.15 and free of PbO are disclosed in U.S. Pat. No. 4,082,427, which is incorporated herein by reference in its entirety.

[0071] The spherical glass beads may be colored as long as they remain transparent. Both colored spherical glass beads made from colored transparent glass and spherical glass beads with a concentric transparent colored coating are encompassed by the present invention. The color may be a natural color resulting from the oxide composition, or may be intentionally selected by adding a component with a specific color. Colored glass beads with a high refractive index and high transparency are disclosed in WO 2014 / 109564.

[0072] Spherical glass beads have a median diameter D50 as measured by laser diffraction. The median diameter D50 is therefore the volume median based on a volume distribution. The median diameter D50 is the diameter below which half of the population of spherical glass beads lies. This volume median diameter is known in the art as Dv50 or D v0.5 It is often said that...

[0073] In a preferred embodiment, the spherical glass beads have a median particle size D50 as measured by laser diffraction of 1.5 to 120 μm, more preferably 2 to 100 μm, even more preferably 3 to 80 μm, and even more preferably 4 to 50 μm, for example 5 to 40 μm or 6 to 30 μm.

[0074] In another embodiment, the spherical glass beads have a median particle size D50 of 10-150 μm, for example 15-150 μm, 20-150 μm, 25-150 μm, 30-150 μm, or 35-150 μm, as measured by laser diffraction.

[0075] In a highly preferred embodiment, the spherical glass beads have a median particle size D50 as measured by laser diffraction of 1 to 100 μm, for example 1 to 75 μm, 1 to 50 μm, 1 to 45 μm, 1 to 40 μm, 1 to 35 μm, 1 to 30 μm, 1 to 25 μm, 1 to 20 μm or 1 to 15 μm.

[0076] The diameters D10 and D90 are known in the art as Dv10 or D v0.1 and Dv90 or D v0.9The D10 diameter is the diameter below which 10% of a population of spherical glass beads lie. Similarly, the D90 diameter is the diameter below which 90% of a population of spherical glass beads lie.

[0077] The span of the particle size distribution of spherical glass beads measured by laser diffraction is

[0078]

number

[0079] In another embodiment, the spherical glass beads have a median particle size D50 of 1 to 100 μm as measured by laser diffraction, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, for example 0 to 0.2 or 0 to 0.1.

[0080] In a preferred embodiment, the spherical glass beads have a median particle size D50 of 1 to 50 μm as measured by laser diffraction, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, for example 0 to 0.2 or 0 to 0.1.

[0081] In another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 to 30 μm as measured by laser diffraction, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, for example 0 to 0.2 or 0 to 0.1.

[0082] In yet another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 to 20 μm as measured by laser diffraction, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, for example 0 to 0.2 or 0 to 0.1.

[0083] In yet another preferred embodiment, the spherical glass beads have a median particle size D50 of 1 to 15 μm as measured by laser diffraction, and a span of 0 to 1.9, preferably 0 to 1.5, more preferably 0 to 1, even more preferably 0 to 0.5, for example 0 to 0.2 or 0 to 0.1.

[0084] As will be appreciated by those skilled in the art, span=0 corresponds to monodisperse spherical glass beads.

[0085] The spherical glass beads are not hemispherically coated with a light-reflective coating. An example of a hemispherical light-reflective coating is a hemispherical metal coating, such as a hemispherical aluminum coating (HAC). The inventors have found that if the spherical glass beads do not protrude from the plastic or polymer matrix, the hemispherical light-reflective coating will adversely affect the retroreflectivity / LIDAR-detectability of one or more outer surface portions (C).

[0086] In a preferred embodiment, the spherical glass beads are not coated with a material that repels polymers. Coated spherical glass beads with a material that repels polymers result in the spherical glass beads levitating, i.e., moving to the outer surface of the spherical glass beads. Therefore, the phrase "coated with a material that repels polymers," as used herein, is considered interchangeable with "coated with a material that results in the spherical glass beads levitating" or "coated with a material that results in the spherical glass beads moving to the outer surface." Such coatings are known in the art. As will be appreciated by those skilled in the art, whether a coating repels a polymer depends on the type of polymer. It is within the knowledge of those skilled in the art to rule out certain coatings for a given polymer based on levitation.

[0087] Examples of polymer-repellent materials that are preferably excluded as coatings for spherical glass beads are: Non-functional silanes, especially (C6-C 10) alkyl or aryl di- or tri-alkoxysilanes, such as hexyltrimethoxysilane, isooctyltrimethoxysilane and phenyltrimethoxysilane, non-functional silicones, especially mixtures of methylhydrogensilicone for buoyancy with silanol-containing compounds for bonding the silicone to spherical glass beads, such as mixtures of methylhydrogensilicone with sodium or potassium methylsiliconate or mixtures of methylhydrogensilicone with low molecular weight silanol-containing polymers; Non-functional fluorochemical materials, such as non-functional fluorochemical polymers is.

[0088] In this context, the expression "non-functional" means "not containing a functional reactive group."

[0089] In one embodiment, the spherical glass beads are coated with a material that improves adhesion to the polymer. Such coatings are known in the art. As will be appreciated by those skilled in the art, whether a coating improves adhesion to a polymer depends on the type of polymer. It is within the knowledge of those skilled in the art to select a preferred coating for a given polymer based on thermomechanical characterization. In this regard, see Gelest's booklet "Silane Coupling Agents - Connecting Across Boundaries," 3, which is incorporated herein by reference in its entirety. rd edition, B. Arkles et al., 2014, Gelest, Inc., Morrisville, PA. Additionally, reference is made to Swarco's brochure, "The game-changing industry system SWARCOFORCE," SWARCO Advanced Industry Systems, Austria, May 2020, which is incorporated herein by reference in its entirety and discloses silane coatings that promote adhesion to many different thermoplastic and thermoset polymers.

[0090] Typical examples of materials that generally improve adhesion to polymers include: functional silanes, such as silanes with mercapto-, glycidoxy- or amino-functional groups; Zirconates, titananates, zircoaluminates, alkyl phosphate esters, functional zirconate molecules, such as zirconate molecules with mercapto-, glycidoxy- or amino-functional groups; functional organosilanes, such as 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane; Functional titanate molecules, such as titanate molecules with mercapto-, glycidoxy-, or amino-functional groups. is.

[0091] In one embodiment, the spherical glass beads are uncoated.

[0092] In a preferred embodiment, the amount of spherical glass beads is 5 to 69 wt.%, more preferably 6 to 68 wt.%, even more preferably 7 to 65 wt.%, for example 8 to 60 wt.%, 9 to 55 wt.% or 10 to 50 wt.%, based on the weight of the three-dimensional plastic product (1).

[0093] In one embodiment, the amount of spherical glass beads is 8 to 68 wt.%, more preferably 12 to 65 wt.%, even more preferably 18 to 60 wt.%, for example 20 to 55 wt.% or 30 to 50 wt.%, based on the weight of the three-dimensional plastic product (1).

[0094] In several embodiments, the amount of spherical glass beads is 4 to 68 wt.%, 4 to 66 wt.%, 4 to 64 wt.%, 4 to 62 wt.%, 4 to 60 wt.%, 4 to 58 wt.%, 4 to 56 wt.%, 4 to 54 wt.%, 4 to 52, or 4 to 50 wt.% based on the weight of the three-dimensional plastic product (1).

[0095] In another embodiment, the amount of spherical glass beads is 5-70 wt.%, 6-70 wt.%, 8-70 wt.%, 10-70 wt.%, 12-70 wt.%, or 14-70 wt.%, based on the weight of the three-dimensional plastic product (1).

[0096] pigment flakes The three-dimensional plastic article comprises 0.1 to 15 wt. % pigment flakes, based on the weight of the three-dimensional plastic article, selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof, wherein the pigment flakes have a median diameter of 1 to 75 μm as measured by laser diffraction.

[0097] Metallic pigment flakes and pearlescent pigment flakes constitute two major types of (flake-like) special effect pigments. Metallic pigment flakes, also called metallic effect pigment flakes, consist of flake-shaped metal particles used to impart metallic effects, color, or functional properties such as corrosion protection, heat resistance, and conductivity to products. The small metal platelets act like mirrors and can reflect incident light. Pearlescent pigment flakes mimic the luster of natural pearls and provide materials with additional color effects such as angular color dependence. Pearlescent pigments typically have several layers of materials with different refractive indices. Thin flakes of low-refractive-index materials, such as mica, silica, alumina, or glass, are typically used as substrates and coated with high-refractive-index materials. However, pearlescent pigment flakes without substrates are also encompassed by the present invention.

[0098] In a preferred embodiment, the pearlescent pigment flakes have several layers of materials with different refractive indices, where a low refractive index material such as mica, silica, alumina or glass is used as the substrate, which is coated with a material with a high refractive index.

[0099] Pigment flake aspect ratio and thickness As used herein, the term "flake" or "platelet" refers to a pigment shape having a large surface area and a small thickness. Typically, a flake or platelet is characterized by its "aspect ratio," which is defined as the largest surface dimension, i.e., the largest diameter, divided by the smallest surface dimension, i.e., the thickness.

[0100] In a preferred embodiment, the pigment flakes used in the present invention have a thickness of less than 1 μm and an aspect ratio (flake diameter / thickness) of at least 10.

[0101] In a preferred embodiment, the thickness of the pigment flakes is from 10 nm to 950 nm, more preferably from 15 nm to 850 nm, and even more preferably from 50 nm to 650 nm.

[0102] In another preferred embodiment, the thickness of the pigment flakes is from 10 nm to 200 nm, for example from 10 nm to 150 nm, from 10 nm to 100 nm, or from 10 to 50 nm.

[0103] In another preferred embodiment, the thickness of the pigment flakes is from 200 nm to 980 nm, for example from 300 nm to 980 nm, from 400 nm to 980 nm, or from 500 nm to 980 nm.

[0104] The pigment flakes used in the present invention preferably have an aspect ratio of at least 12, preferably at least 15, more preferably at least 20, and even more preferably at least 30.

[0105] In one embodiment, the pigment flakes used in the present invention have an aspect ratio of 10-500, preferably 15-250, and more preferably 20-100.

[0106] Pigment flake median diameter In a preferred embodiment, the median diameter of the pigment flakes is 1.5 to 65 μm, more preferably 2 to 50 μm, even more preferably 3 to 40 μm, for example 4 to 35 μm, or 5 to 30 μm.

[0107] In another preferred embodiment, the pigment flakes have a median diameter of 1 to 65 μm, for example 1 to 50 μm, 1 to 40 μm, 1 to 35 μm, 1 to 25 μm, 1 to 20 μm, 1 to 15 μm or 1 to 13 μm.

[0108] In yet another preferred embodiment, the median diameter of the pigment flakes is from 2 to 75 μm, for example from 5 to 75 μm, 10 to 75 μm, 15 to 75 μm, 20 to 75 μm, 25 to 75 μm, 30 to 75 μm or 35 to 75 μm.

[0109] Types of pigment flakes In a preferred embodiment, the pigment flakes defined herein are selected from (I), (II), (III) or combinations thereof: (I) optionally coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, BO, GeO2, MgF2, metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and a binder; Metal flakes or mica flakes, (II) Flakes comprising Al2O3, SiO2, glass, ceramic, graphite or mica platelets coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, BO, GeO2, metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders; and (III) Flakes comprising Al2O3 platelets doped with one or more elements selected from the group consisting of TiO2, ZrO2, SiO2, SnO2, In2O3, ZnO and iron oxides, coated with at least one layer of one or more elements selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, BO3, GeO2, metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and a binder.

[0110] In a preferred embodiment, the pigment flakes are synthetic pigment flakes. As will be appreciated by those skilled in the art, the term "synthetic" in "synthetic pigment flakes" means that the pigment flakes are not naturally occurring pigment flakes, but are chemically manufactured pigment flakes or naturally occurring pigment flakes that have been chemically / physically processed to modify their properties. One advantage of using synthetic pigment flakes is that they can be produced with very smooth surfaces and high aspect ratios, thereby increasing their reflective properties.

[0111] The pigment flake (I) can have zero to many coating layers, for example, 1, 2, 3, 4, or 5 coating layers. In one embodiment, the metal of the metal pigment flake (I) is selected from the group consisting of aluminum, silver, and gold, preferably aluminum. In one embodiment, the metal pigment flake (I) is an aluminum flake without a coating. In one embodiment, the pigment flake (I) is a mica flake without a coating. In one embodiment, the pigment flake (I) is a mica flake with several coating layers, for example, a mica flake coated with TiO2, Fe2O3, and SnO2.

[0112] In one embodiment, the metal pigment flake (I) is an aluminum pigment flake coated with at least one layer of one or more components selected from the group consisting of metal oxides, SiO2, B2O3, and GeO2. In one embodiment, the metal pigment flake (I) is an aluminum flake coated with a SiO2 layer.

[0113] In one embodiment, the flakes (I) are coated with a SiO2 layer and an outer layer comprising one or more colorants and a binder for fixing the one or more colorants.

[0114] Examples of metal oxides that can be applied to the coating layer of the metal pigment flakes (I) are selected from the group consisting of TiO2, ZrO2, SnO2, ZnO, MnO2, MgO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, CO3O4, VO2, V2O3, NiO, and combinations thereof.

[0115] Examples of suitable aluminum pigment flakes (I) coated with (i) a first layer of SiO2, B2O3, MnO2, MgO, GeO2, or Al2O3, (ii) a second Fe2O3 layer on the first layer, and optionally (iii) a third layer of TiO2, ZrO2, or Al2O3 on the second layer are disclosed in U.S. Patent Application Publication No. 2019 / 044679, which is incorporated herein by reference in its entirety.

[0116] The pigment flakes (II) and (III) can have one to many coating layers, for example 2, 3, 4 or 5 coating layers.

[0117] Examples of metal oxides that can be applied to the coating layer of the metal pigment flakes (I) are selected from the group consisting of TiO2, ZrO2, SnO2, ZnO, MnO2, MgO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, CO3O4, VO2, V2O3, NiO, and combinations thereof.

[0118] In one embodiment, the pigment flakes (II) comprise glass platelets, and the glass is borosilicate glass. In a highly preferred embodiment, the pigment flakes (II) comprise Al2O3 platelets.

[0119] In one embodiment, the pigment flakes (II) or (III) are coated with one or more layers of a metal oxide, for example at least one layer of a metal oxide selected from the group consisting of TiO2, ZrO2, SnO2, ZnO, MnO2, MgO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, CO3O4, VO2, VO3, NiO, and combinations thereof. In a preferred embodiment, the pigment flakes (II) or (III) are coated with one or more layers of a metal oxide selected from the group consisting of TiO2, Fe2O3, Fe3O4, SnO2, ZrO2, Cr2O3, and combinations thereof, for example coated with one layer of a metal oxide selected from the group consisting of TiO2, Fe2O3, and combinations thereof.

[0120] Examples of pigment flakes (II) comprising Al2O3 platelets coated with various layers of metal oxide, SiO2, and organic dye as topcoats are disclosed in EP 2799398, the entire contents of which are incorporated herein by reference.

[0121] An example of pigment flake (II) comprising Al2O3 platelets coated with a metal oxide selected from the group consisting of TiO2, Fe2O3, and combinations thereof, and its preparation is disclosed in U.S. Pat. No. 6,267,810, which is incorporated herein by reference in its entirety.

[0122] In another embodiment, the pigment flakes (II) or (III) are titanium suboxide [Ti n O 2n-1(where n is an integer greater than 1), for example with a layer of an oxide such as Ti3O5, Ti2O3, with a layer of titanium oxynitride, with a layer of FeO(OH), or with a thin semi-transparent metal layer comprising, for example, Al, Fe, Cr, Ag, Au, Pt or Pd, or a combination thereof.

[0123] In yet another embodiment, the pigment flakes (II) or (III) are coated with a layer of a metal sulfide, for example a sulfide of tungsten, molybdenum, cerium, lanthanum or a rare earth element.

[0124] In another embodiment, the pigment flakes (II) or (III) are coated with one or more colorants, such as Prussian blue or carmine red, and an outer layer of a binder to fix the colorants.

[0125] As will be appreciated by those skilled in the art, these various layers can be combined, provided that the colorant and binder layer(s), if present, are always the outer layers.

[0126] Examples of metal oxide coated pigment flakes (III) comprising titanium oxide doped Al2O3 platelets and their preparation are disclosed in EP 0 763 573, which is incorporated herein by reference in its entirety.

[0127] Examples of metal oxide coated pigment flakes (III) comprising platelets of TiO, ZrO, SiO, SnO, InO or ZnO doped AlO are disclosed in EP 2799398, which is incorporated herein by reference in its entirety.

[0128] Ratio of pigment flake diameter to spherical glass bead diameter The inventors have found that a higher ratio of the median diameter of the pigment flakes to the median diameter D50 of the spherical glass beads improves retroflection and LIDAR-detectability.

[0129] In preferred embodiments, the median diameter of the pigment flakes is greater than 35% of the median particle size D50 of the spherical glass beads, more preferably greater than 38%, such as greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 70%, greater than 90%, greater than 110%, or greater than 130%.

[0130] In another preferred embodiment, the median diameter of the pigment flakes is 35 to 400%, more preferably 40 to 400%, such as 45 to 400%, 50 to 400%, 55 to 400%, 60 to 400%, 70 to 400%, 90 to 400%, 110 to 400%, or 130 to 400% of the median particle diameter D50 of the spherical glass beads.

[0131] In still yet another embodiment, the median diameter of the pigment flakes is 35 to 350%, more preferably 35 to 300%, such as 35 to 250%, 35 to 225%, 35 to 200%, 35 to 175%, 35 to 150%, 35 to 125%, 35 to 100%, or 35 to 75% of the median particle size D50 of the spherical glass beads.

[0132] Amount of pigment flakes In a preferred embodiment, the amount of said pigment flakes is 0.15 to 13 wt.%, for example 0.3 to 10 wt.%, 0.5 to 7.5 wt.%, 0.8 to 7 wt.%, 0.9 to 6.5 wt.% or 1 to 6 wt.%, based on the weight of the three-dimensional plastic product (1).

[0133] In one embodiment, the amount of pigment flakes is 0.1 to 14 wt.%, for example 0.1 to 12 wt.%, 0.1 to 10 wt.%, 0.1 to 8 wt.%, 0.1 to 5 wt.%, or 0.1 to 4 wt.%, based on the weight of the three-dimensional plastic product (1).

[0134] In another embodiment, the amount of the pigment flakes is 0.2 to 15 wt.%, for example 0.5 to 15 wt.%, 1 to 15 wt.%, 2 to 15 wt.%, 3 to 15 wt.%, or 4 to 15 wt.%, based on the weight of the three-dimensional plastic product (1).

[0135] The amount of the pigment flakes is preferably 1 part by weight per 1 to 80 parts by weight of the spherical glass beads, preferably 1 part by weight per 1 to 40 parts by weight of the spherical glass beads, and more preferably 1 part by weight per 1 to 30 parts by weight of the spherical glass beads.

[0136] Further ingredients As defined hereinabove, the three-dimensional plastic product (1) comprises 0-15 wt.% of one or more additional components based on the weight of the three-dimensional plastic product (1). As will be understood by those skilled in the art, the "additional" components are different from the other defined components in the three-dimensional plastic product (1). In other words, the one or more additional components do not include the polymer (thermoplastic or thermoset), the spherical glass beads, and the pigment flakes.

[0137] In a preferred embodiment, the one or more further components are: Spherical glass beads coated with a light-reflective coating, Spherical glass beads having a refractive index of not more than 1.93 measured at a wavelength of 589 nm, and Spherical glass beads coated with a polymer-repellent material does not include one or more of:

[0138] The one or more additional components can include any additive typically used in plastic products. In one embodiment, the additional component is selected from the group consisting of rheology modifiers, foam control agents, luminescent agents, UV-absorbers, plasticizers, reinforcing fibers, preservatives, dyes, cure initiators, organic pigments, inorganic pigments other than metal pigment flakes and pearlescent pigment flakes, and combinations thereof. Examples of reinforcing fibers are glass, carbon, aramid, and basalt fibers.

[0139] In one embodiment, the amount of one or more further components is 0.01 to 15 wt.%, 0.02 to 13 wt.%, 0.05 to 11 wt.%, 0.1 to 10 wt.%, 0.2 to 9 wt.%, 0.25 to 8 wt.%, 0.30 to 7 wt.% or 0.35 to 6 wt.% based on the weight of the three-dimensional plastic product (1).

[0140] In another embodiment, the amount of one or more further components is 0-14 wt.%, 0-13 wt.%, 0-12 wt.%, 0-11 wt.%, 0-10 wt.%, 0-9 wt.%, 0-8 wt.% or 0-7 wt.% based on the weight of the three-dimensional plastic product (1).

[0141] In still yet another embodiment, the amount of one or more further components is 0.02-15 wt.%, 0.05-15 wt.%, 0.1-15 wt.%, 0.2-15 wt.%, 0.25-15 wt.%, 0.30-15 wt.% or 0.35-15 wt.% based on the weight of the three-dimensional plastic product (1).

[0142] Modified 3D Products(2) The three-dimensional plastic product (1) according to the first aspect consists of the composition defined hereinabove, which can be used as an intermediate in the production of a modified three-dimensional product (2) having one or more further parts or components (3) attached thereto.

[0143] In a second aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: one or more three-dimensional plastic products (1) according to the first aspect and one or more further parts or components (3) attached thereto, or one or more further parts or components (3) and one or more three-dimensional plastic products (1) according to the first aspect attached thereto; wherein at least a portion of one or more outer retroreflective surface portions (C) of the three-dimensional plastic product (1) according to the first aspect is not covered by one or more further parts or components (3).

[0144] Thus, one or more three-dimensional plastic products (1) according to the first aspect can be part of a modified three-dimensional product (2) to provide retroreflectivity and / or LIDAR-detectability to the modified product. As an example, the three-dimensional plastic product (1) according to the first aspect is a bumper that is part of a vehicle, and the vehicle is the modified three-dimensional product (2).

[0145] The one or more further parts or components (3) are not necessarily made of plastic, for example, if the modified three-dimensional product (2) is a car and the three-dimensional plastic product (1) is two mirror housings, the one or more further parts or components (3) attached to the two mirror housings can be the remaining car parts, such as rubber tires, metal body and chassis, etc.

[0146] In a preferred embodiment, the modified three-dimensional product (2) comprises a three-dimensional plastic product (1) according to the first aspect, part of which is coated with one or more coating layers, which one or more coating layers being one or more further parts or components (3).

[0147] In a preferred embodiment, the modified three-dimensional product (2) is a vehicle part, more preferably a body part, such as a body part selected from the group consisting of a bumper, a mirror housing, a handle, a radio antenna, and a skirting.

[0148] In a highly preferred embodiment, the modified three-dimensional product (2) is a vehicle, more preferably a vehicle selected from the group consisting of a car, a lorry, a truck, a bike, a moped, a scooter, a motorcycle, a train, a tram, a boat, a watercraft, a drone, a skateboard, a missile, a helicopter and an aircraft, even more preferably a vehicle selected from a car, a lorry, a truck, a bike, a moped, a scooter and a motorcycle.

[0149] Method for producing three-dimensional plastic products (1) A third aspect of the present invention is a method for producing a three-dimensional plastic article (1) with retroreflective properties according to the first aspect, in which the polymer is a thermoplastic polymer, comprising: (a) providing a thermoplastic polymer, spherical glass beads, pigment flakes, and optional additional ingredients; (b) blending the components provided in step (a) at a temperature above the melting point of the thermoplastic polymer; (c) feeding the mixture obtained in step (b) into a die or extruding the mixture obtained in step (b); (d) cooling the mixture in the mold to a temperature below the melting point of the thermoplastic polymer and removing the three-dimensional plastic article (1) with retroreflective properties from the mold, or cooling the extrudate to a temperature below the melting point of the thermoplastic polymer to provide a three-dimensional plastic article (1) with retroreflective properties. The present invention relates to a method, comprising:

[0150] In one embodiment, the process according to the third aspect is carried out in an extruder and injection molding machine. Choosing appropriate process conditions is within the knowledge of one skilled in the art.

[0151] As will be appreciated by those skilled in the art, step (b) of compounding the ingredients can be carried out in more than one step, for example, by first preparing a masterbatch of polymer and spherical glass beads, e.g., in filament or pellet form, and then compounding this masterbatch with pigment flakes, optionally one or more further ingredients, and optionally additional polymers.

[0152] A fourth aspect of the present invention is a method for producing a three-dimensional plastic product (1) with retroreflective properties according to the first aspect, in which the polymer is a thermoset polymer, comprising: (a) providing a thermosettable resin, spherical glass beads, pigment flakes, and optional additional ingredients; (b) mixing the ingredients provided in step (a); (c) feeding the mixture obtained in step (b) into a mold; (d) curing the mixture in the mold to provide a three-dimensional plastic article (1) with retroreflective properties; (e) removing the three-dimensional plastic product (1) with retroreflective properties from the mold; The present invention relates to a method, comprising:

[0153] In one embodiment, the method according to the fourth aspect is carried out in an injection molding machine. Choosing appropriate process conditions is within the knowledge of one skilled in the art.

[0154] As described above, one or more outer retroreflective surface portions (C) of the three-dimensional plastic article (1) can be smooth or can have a glossy or semi-glossy appearance, with the spherical glass beads being completely embedded in the polymer matrix. Such three-dimensional plastic articles (1) can be produced using a mold with a smooth inner surface by the method according to the third or fourth embodiment. One or more outer retroreflective surface portions (C) of the three-dimensional plastic article (1) can also be rough or can have a matte appearance, with the spherical glass beads protruding from the surface but still covered by the polymer matrix. Such three-dimensional plastic articles (1) can be produced using a mold with a rough inner surface by the method according to the third or fourth embodiment.

[0155] Method for producing modified three-dimensional products (2) As will be appreciated by those skilled in the art, the modified three-dimensional product (2) as defined herein above can be produced by providing one or more three-dimensional plastic products (1) according to the first aspect and one or more further parts or components (3) and combining, joining or assembling them.

[0156] If the one or more further parts or components (3) are also plastic components such as thermoplastic polymers, the modified three-dimensional product (2) defined herein above can be produced by co-extrusion of (i) a melt of the polymer, spherical glass beads, pigment flakes and optional further components as defined in relation to the first aspect, in the relative amounts as defined in relation to the first aspect, and (ii) one or more further polymers to form the one or more further plastic parts or components (3).

[0157] As will be appreciated by those skilled in the art, a modified three-dimensional product (2) comprising one or more three-dimensional plastic products (1) according to the first aspect produced using co-extrusion and one or more further plastic parts or components (3) can then be provided with further parts or components (3) to provide another modified three-dimensional product (2).

[0158] Laser Imaging Detection and Ranging (LIDAR) Method A fifth aspect of the present invention is a method for laser imaging detection and ranging (LIDAR) of a three-dimensional plastic product (1) according to the first aspect or a modified three-dimensional product (2) according to the second aspect, comprising: (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver and optionally a global positioning system (GPS); (ii) transmitting electromagnetic radiation from an electromagnetic radiation source of a LIDAR device to the three-dimensional plastic product (1) or the modified three-dimensional product (2); (iii) scanning the electromagnetic radiation reflected by the three-dimensional plastic product (1) or the modified three-dimensional product (2) with a receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation, preferably as a function of time; the distance between the three-dimensional plastic product (1) or the modified three-dimensional product (2) and the LIDAR device; Acceleration of the three-dimensional plastic product (1) or the modified three-dimensional product (2), Deceleration of the three-dimensional plastic product (1) or modified three-dimensional product (2), The direction of movement of the three-dimensional plastic product (1) or the modified three-dimensional product (2), the velocity of the three-dimensional plastic product (1) or the modified three-dimensional product (2), preferably relative to the velocity of the LIDAR device, and 3D images of three-dimensional plastic products (1) or modified three-dimensional products (2) and computing one or more of: The present invention relates to a method, comprising:

[0159] As will be appreciated by those skilled in the art, computation of the velocity, acceleration, deceleration and direction of movement of the three-dimensional plastic article (1) or modified three-dimensional article (2) requires that steps (ii) and (iii) be performed as a function of time.

[0160] If the LIDAR device is also equipped with GPS, the distance between the three-dimensional plastic product (1) or the modified three-dimensional product (2) and the LIDAR device can also be displayed on the map, and a 3D image of the three-dimensional plastic product (1) or the modified three-dimensional product (2) can be confirmed on the map.

[0161] In a preferred embodiment, the electromagnetic radiation transmitted and scanned in steps (ii) and (iii), respectively, has a wavelength of 740 to 2500 nm, more preferably 750 to 1800 nm, even more preferably 780 to 1600 nm, for example 905 nm or 1550 nm.

[0162] In one embodiment, the electromagnetic radiation transmitted and scanned in steps (ii) and (iii), respectively, has a wavelength of 740 to 2200 nm, for example, 740 to 2000 nm, 740 to 1800 nm, 740 to 1700 nm, 740 to 1650 nm, or 740 to 1600 nm.

[0163] In another embodiment, the electromagnetic radiation transmitted and scanned in steps (ii) and (iii), respectively, has a wavelength of 750 to 2500 nm, for example, 780 to 2500 nm, 800 to 2500 nm, 825 to 2500 nm, 850 to 2500 nm, and 875 to 2500 nm.

[0164] use In a sixth aspect, the present invention relates to the use of a three-dimensional plastic product (1) according to the first aspect in the form of filaments or pellets, wherein the polymer is a thermoplastic polymer, in the production of a ready-to-use three-dimensional plastic product (1) according to the first aspect, wherein the polymer is a thermoplastic polymer.

[0165] In a seventh aspect, the present invention relates to a three-dimensional plastic product (1) according to the first aspect or a modified three-dimensional product (2) according to the second aspect, in laser imaging detection and ranging (LIDAR) of the three-dimensional plastic product (1) or the modified three-dimensional product (2), and / or to improve the visibility of the three-dimensional plastic product (1) or the modified three-dimensional product (2) under visible light conditions, and / or for preparing a three-dimensional image of said three-dimensional plastic product (1) or said modified three-dimensional product (2) Regarding use.

[0166] While the present invention has been described with reference to certain specific embodiments set forth above, it will be recognized that there are various modifications and alternative forms to these embodiments that will be known to those skilled in the art.

[0167] Also, for the proper understanding of this document and its claims, the verb "comprise" and its conjugations should be understood to be used in its open-ended sense, meaning that items following the word are included, but items not specifically mentioned are not excluded. In addition, a reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one of that element is present, unless the context clearly requires that there is one and only one of that element. Thus, the indefinite article "a" or "an" usually means "at least one."

[0168] [Example] material spherical glass beads Micro glass beads (C) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, had a refractive index of about 2.2 measured at a wavelength λ of 589 nm, and a median particle size D50 of about 40.37 μm, a D10 diameter of 37.32 μm, and a D90 diameter of 44.11 μm measured by laser diffraction.

[0169] Micro glass beads (CS) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, had a refractive index of about 2.2 measured at a wavelength λ of 589 nm, and a median particle size D50 of about 27.49 μm, a D10 diameter of 20.64 μm, and a D90 diameter of 33.24 μm measured by laser diffraction.

[0170] Micro glass beads (CSS) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, had a refractive index of about 2.2 measured at a wavelength λ of 589 nm, and a median particle size D50 of 22.00 μm, a D10 diameter of 16.33 μm, and a D90 diameter of 26.21 μm measured by laser diffraction.

[0171] Micro glass beads (CSTL) obtained from Swarco, Austria, having a refractive index of about 2.1 measured at a wavelength λ of 589 nm, and a median particle size D50 of 7.80 μm, a D10 diameter of 3.27 μm and a D90 diameter of 20.2 μm as measured by laser diffraction.

[0172] HAC-coated micro glass beads (CSX) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, had a refractive index of about 2.2 measured at a wavelength λ of 589 nm, and a median particle size D50 of 26.46 μm, a D10 diameter of 22.94 μm, and a D90 diameter of 29.57 μm measured by laser diffraction.

[0173] HAC-coated micro glass beads (NSX) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., China, had a refractive index of approximately 1.9 measured at a wavelength λ of 589 nm, and a median particle size D50 of 26.13 μm, a D10 diameter of 19.51 μm, and a D90 diameter of 31.41 μm measured by laser diffraction.

[0174] polymer Polypropylene homopolymer (PP) obtained from Sabic Polystyrene pellets (PS) obtained from Total Low density polyethylene (LDPE) granules obtained from Sabic High density polyethylene (HDPE) pellets obtained from Lyondell Basell

[0175] Further ingredients Pigment White 6 U.5.1031.m Blue PO72-Orange Pigment PZ125 black PZ810 / 50 Black SINLOIHI FZ-6014 Orange (“SINL”) obtained from Sinloihi Co., Ltd., Japan.

[0176] pigment flakes KCPP® KC123, available from Kuncai Americas, (mica, TiO2 and SnO2), pearlescent effect pigment in silver-white shade, 5-30 μm, Xillamaya T60-23 SW Galaxy Blue, available from Fujian Kuncai Material Technology, synthetic mica pearlescent pigment flakes, 6-30μm Xillamaya T60-10 SW, obtained from Fujian Kuncai Material Technology, (synthetic fluorphlogopite, TiO2, SnO2, SiO2, Ce2O3), D 50 Diameter 14.5μm ("Xillam.") Iriodin® 9307 Star Gold SW, available from Merck KgaA, (mica, TiO2, SiO2, Fe2O3 and SnO2, auxiliary), D 50 Diameter 21~26μm Mastersafe MP 35-20B, available from Eckart GmbH, aluminum pigment flakes, D 50 Diameter 35μm KC 8200 10-45 μm, obtained from Fujian Kuncai Material Technology, (synthetic fluorphlogopite, TiO2), D 50 Diameter 20.0μm Xirallic® NXT M260-70 SW Amur Black, available from Merck KGaA, (Fe3O4, Al2O3, SiO2, auxiliary), D 50 Diameter 17~23μm Alegrace® Aurous B 21 / 11-1 Yellow Gold flakes, available from Schlenk Metallic Pigments, 8-38 μm Aluminum paste Chromos ON / 08-01, available from Schlenk Metallic Pigments GmbH, surface-treated aluminum pigment flakes, D 50 Diameter 8μm Zenexo® Copperglow WB 21 OO, available from Schlenk Metallic Pigments GmbH, D 50 Diameter 21μm Zenexo® Golden Shine WB 21 YY, available from Schlenk Metallic Pigments GmbH, D 50 Diameter 21μm Mastersafe MP 68-20B, aluminum pigment flake, available from Eckart GmBH, D 50 Diameter 68μm ("Master.") STAPA PP REFLEXAL 1032 / 80, aluminum silverdollar pigment, available from Eckart GmBH, D 50 Diameter 10μm (“STAPA”) Grandal® P 3600, available from Carl Schlenk AG, D 50 Diameter 31μm (“P3600”)

[0177] Example 1: Preparation of three-dimensional colored plastic products Eighteen kinds of three-dimensional colored plastic products were prepared from the ingredients shown in Tables 1 and 2 as follows.

[0178] First, the monoconcentrate was prepared by adding the relevant plastic pellets (PP or LDPE) to a twin-screw extruder (Noris ZSC 20), heating to melt the polymer, and adding the relevant glass beads to the molten plastic mixture via a side feeder, followed by thorough mixing. The resulting strands were cooled and pelletized to form the monoconcentrate.

[0179] In a second step, the monoconcentrates were combined with various color pigments and pigment flakes at various concentrations to obtain 18 final formulations (see Tables 1 and 2 for the overall composition of the 18 final formulations). These final formulations were made using a single-screw extruder (Noris ESE30) by adding the relevant monoconcentrates, relevant color pigments and pigment flakes, and optionally additional polymer (PP or LDPE). The component mixture was briefly blended by hand shaking / stirring for 1 minute, added to the extruder, and heated to an elevated temperature to melt and mix. The resulting strands were cooled and pelletized to produce pellets of the final formulations.

[0180] In the third step, product pellets of the relevant final formulation were added to an injection molding machine (ALLROUNDER 320 C 500-100), heated, and extruded into a mirror-like mold shape to produce plastic products with a length of 10 cm, a width of 5 cm, and three regions with different thicknesses (2 mm, 3 mm, and 4 mm) along the length. All three-dimensional colored plastic products, i.e., those containing spherical glass beads, had a very smooth outer surface. The glass beads did not protrude from the outer surface; i.e., the surface was not rough (ungrained).

[0181] [Table 1]

[0182] [Table 2]

[0183] Example 2: Evaluation of retroreflectivity and LIDAR-detectability The overall (off-center) retroreflection of the 18 three-dimensional colored plastic products produced in Example 1 was evaluated by visually inspecting the product with a torch beam directed at an angle of 30° from an axis normal to the major surface of the three-dimensional colored plastic product, with the line of sight substantially aligned with the torch beam, to visually determine whether retroreflection was observed and its degree.

[0184] A grade of "1" means very little to no warping, and a grade of "4" means very good retroreflection. Details are shown in Table 3. As can be inferred from Table 3, the retroreflection of the three-dimensional colored plastic product according to the present invention is much better than that of the comparative product. The warping of the surface of the three-dimensional colored plastic product according to the present invention is good to very good.

[0185] LIDAR detectability was determined by scanning the surfaces of the 18 three-dimensional colored plastic products produced in Example 1 with a Livox Tele-15 LIDAR device (Livox Technology Company Co., Ltd.) at a wavelength of 905 nm at an angle of approximately 30° to the axis perpendicular to the main surface. Scanning was performed under daylight conditions. The Tele-15 LIDAR device was installed at a distance of approximately 20 meters from the main surface of the three-dimensional colored plastic product. The Tele-15 LIDAR device calculated reflectance values ​​for various areas of the main surface of the scanned three-dimensional colored plastic product based on the ratio of reflected laser energy to incident laser energy, and a point cloud was created from these data. Every point in the point cloud had a corresponding reflectance value. The reflectance values ​​obtained for each three-dimensional colored plastic product were ranked from lowest to highest, and the highest value was designated as the reflectance score (reference value) for that product. Because all scanned products were identical in terms of morphology and scanned at the same angle and distance, their LIDAR detectability could be compared by comparing their reflectance scores. The resulting reflectance scores are shown in Table 3.

[0186] As can be inferred from Table 3, the LIDAR-detectability is much better for the three-dimensional colored plastic product according to the invention than for the comparative product.

[0187] [Table 3]

[0188] Example 3: Production of 3D plastic products Three-dimensional plastic products were prepared as follows: In the first step, five monoconcentrates (MC1 to MC5) were prepared with the recipes shown in Table 4.

[0189] [Table 4] The monoconcentrates were prepared by adding the relevant plastic pellets to a twin-screw extruder (Noris ZSC 20), heating to 150°C (LDPE) or 200°C (PS), and adding the relevant glass beads to the molten plastic mixture via a side feeder, followed by thorough mixing. The resulting strands were cooled and pelletized to form the monoconcentrates.

[0190] In a second step, the monoconcentrate was combined with various color pigments and pigment flakes in various concentrations and combinations to obtain 43 final formulations (V1-V43). These final formulations were made using a single-screw extruder (Noris ESE30) by adding the relevant monoconcentrate, the relevant pigment / pigment flake, and sufficient additional high-density polyethylene (HDPE) or polystyrene (PS). The component mixtures were briefly blended by handshaking / stirring for 1 minute, added to the extruder, and heated to 200°C to melt and mix. The resulting strands were cooled and pelletized to produce the final formulations.

[0191] In the third step, product pellets of the relevant final formulation were added to an injection molding machine (ALLROUNDER 320 C 500-100) and heated to 200-220°C before being extruded into a mirror-like mold shape to produce three-dimensional plastic products with a length of 10 cm, a width of 5 cm, and three regions of different thicknesses (2 mm, 3 mm, and 4 mm) along the length. All three-dimensional plastic products, i.e., those containing spherical glass beads, had very smooth outer surfaces. The glass beads did not protrude from the outer surface; i.e., the surface was not rough.

[0192] The recipes for the 43 final formulations V1 to V43 are shown in Table 5.

[0193] [Table 5] [Table 6]

[0194] Example 4: Comparative Example According to the Prior Art Final formulation V40 conforms to Example 1 of WO 2005 / 033194. Final formulation V41 conforms to Comparative Example A of WO 2005 / 033194. The formulations in the examples of WO 2005 / 033194 contain 38 μm HAC-coated BaTiO microspheres and 8.5 μm uncoated BaTiO microspheres obtained from Prizmalite Industries. As explained above, the spherical glass beads of WO 2005 / 033194 have a refractive index of 1.9. However, final formulations V40 and V41 contain 7.8 μm uncoated microspheres with a refractive index of 2.1. However, this does not affect the conclusions that can be drawn from the results.

[0195] See Table 6 below for a summary of the recipes. The retroreflectance of the non-textured surface of the product produced from final formulation V40 according to the examples of WO 2005 / 033194 was approximately 30-50% higher than the retroreflectance of the non-textured surface of the product produced from final formulation V41 according to the "qualitative opinion of a person skilled in the art."

[0196] The retroreflection of three-dimensional plastic articles produced from final formulations V40 and V41 (both not according to the present invention) was visually evaluated using a torch light at a 45° angle with respect to an axis perpendicular to the major surfaces of the plastic articles. The viewing angle was along the direction of the torch light, i.e., also at a 45° angle with respect to an axis perpendicular to the major surfaces of the three-dimensional plastic articles. From the visual evaluation, it was concluded that the non-textured surface of the three-dimensional plastic article produced from final formulation V40 (according to Example 1 of WO 2005 / 033194) exhibited 30-50% better, but less, retroreflection than the non-textured surface of the three-dimensional plastic article produced from final formulation V41 (according to Comparative Example A of WO 2005 / 033194). See Table 6.

[0197] Furthermore, the non-textured surfaces of both the three-dimensional plastic article produced from final formulation V40 and the three-dimensional plastic article produced from final formulation V41 showed insufficient retroreflection to be of any relevance at an angle of 45°. This result would be even worse if final formulations V40 and V41 contained carbon black pigment (as applied in Example 1 and Comparative Example A of WO 2005 / 033194).

[0198] Table 6 also summarizes the recipes for final formulations V15, V17, and V35. The retroreflectivity of the three-dimensional plastic articles produced from final formulations V15, V17, and V35 (all in accordance with the present invention) was also visually evaluated using a torch light at a 45° angle to an axis normal to the major surfaces of the three-dimensional plastic articles. As shown in Table 6, the non-textured surfaces of the three-dimensional plastic articles produced from final formulations V15, V17, and V35 demonstrate significantly higher retroreflectivity than the non-textured surfaces of the three-dimensional plastic articles produced from final formulations V40 and V41.

[0199] The LIDAR detectability of the surfaces of the three-dimensional plastic products made from the final formulations V40, V41, V15, V17, and V35 was determined by scanning the main surfaces of the three-dimensional plastic products at a wavelength of 905 nm at an angle of approximately 30° to the axis perpendicular to the main surfaces using a Livox Tele-15 LIDAR device (Livox Technology Company Co., Ltd.). Scans were performed under daylight conditions. The Tele-15 LIDAR device was placed at a distance of approximately 17 meters from the main surfaces of the three-dimensional plastic products.

[0200] The Tele-15 LIDAR device calculates reflectance values ​​for various areas of the scanned surface based on the ratio of reflected to incident laser energy, and creates a point cloud from these data. Every point in the point cloud has a corresponding reflectance value. The reflectance values ​​obtained for each 3D plastic product were ranked from lowest to highest, and the highest value was designated as the reflectance score (reference value) for that product. Because all scanned products were identical in terms of morphology and scanned at the same angle and distance, their LIDAR detectability could be compared by comparing their reflectance scores. The resulting reflectance scores are shown in Table 6.

[0201] It was concluded that the primary surface of the three-dimensional plastic article produced from final formulation V40 (according to Example 1 of WO 2005 / 033194) has lower LIDAR-detectability than the primary surface of the three-dimensional plastic article produced from final formulation V41 (according to Comparative Example A of WO 2005 / 033194). As shown in Table 6, the primary surfaces of the three-dimensional plastic articles produced from final formulations V15, V17 and V35 demonstrate significantly higher LIDAR-detectability than the primary surfaces of the three-dimensional plastic articles produced from final formulations V40 and V41.

[0202] [Table 7]

[0203] Example 5: Retroreflectivity and LIDAR-detectability of 3D plastic products The retroreflectivity and LIDAR-detectability of the surfaces of three-dimensional plastic articles produced from several final formulations selected from V1 to V43 were tested using the method defined in Example 4. The results of the retroreflectivity tests are shown in Figure 7, which shows the retroreflectivity of the surfaces of 20 articles (4 rows, 5 columns). The characteristics of the various final formulations used in this test are briefly summarized in Table 7. The Lidar reflectivity scores are also shown in Table 7.

[0204] [Table 8]

[0205] From a comparison of Figure 7 and columns 2-5 of Table 7, it can be concluded that the final formulation containing uncoated spherical glass beads (CSS or CSTL) with a high refractive index of 2.2 / 2.1 in combination with pigment flakes provides the highest retroreflection, whereas the final formulation containing HAC-coated spherical glass beads (NSX or CSX) with a refractive index of 1.9 or 2.2 in combination with pigment flakes exhibits almost no retroreflection. Thus, the HAC coating significantly reduces retroreflection in products where the spherical glass beads do not protrude from the polymer matrix. Furthermore, from a comparison of Table 7, it can be concluded that the final formulation containing uncoated spherical glass beads (CSS or CSTL) with a high refractive index of 2.2 / 2.1 in combination with pigment flakes provides much higher LIDAR detectability in products where the spherical glass beads do not protrude from the polymer matrix than the final formulation containing HAC-coated spherical glass beads (NSX or CSX) with a refractive index of 1.9 or 2.2 in combination with pigment flakes.

Claims

1. A three-dimensional plastic product (1) having an outer surface (A), at least a portion (B) of the outer surface (A) having retroreflective properties, the three-dimensional plastic product (1) having, based on the total weight of the three-dimensional plastic product (1): 25 to 95.9 wt. % of a polymer selected from thermoplastic polymers and thermoset polymers; 4 to 70 wt. % spherical glass beads, having a median particle size D50 of 1 to 150 μm as measured by laser diffraction and a refractive index of 2.0 to 2.8 as measured at a wavelength λ of 589 nm, wherein the spherical glass beads are not hemispherically coated with a light-reflective coating; 0.1 to 15 wt. % of pigment flakes selected from the group consisting of metallic pigment flakes, pearlescent pigment flakes, or combinations thereof, having a median diameter of 1 to 75 μm as measured by laser diffraction, preferably a thickness of less than 1 μm and an aspect ratio (flake diameter / thickness) of at least 10, and 0-15 wt. % of one or more further ingredients, The smallest dimension of the plastic product (1) is at least 500 μm in all directions, The outer retroreflective portion (B) includes one or more outer retroreflective surface portions (C) where the spherical glass beads do not protrude from the polymer matrix. Three-dimensional plastic products (1).

2. 2. The three-dimensional plastic product (1) according to claim 1, wherein the median diameter of the pigment flakes is greater than 35%, preferably greater than 38%, such as greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 70%, greater than 90%, greater than 110%, or greater than 130% of the median particle size D50 of the spherical glass beads.

3. 3. The three-dimensional plastic product (1) according to claim 1 or 2, wherein the amount of said pigment flakes is 1 part by weight for 1 to 80 parts by weight of said spherical glass beads, preferably 1 part by weight for 1 to 40 parts by weight of said spherical glass beads, more preferably 1 part by weight for 1 to 30 parts by weight of said spherical glass beads.

4. said one or more further ingredients being Spherical glass beads coated with a light-reflective coating, spherical glass beads having a refractive index of 1.93 or less measured at a wavelength of 589 nm; and Spherical glass beads coated with a polymer-repellent material A three-dimensional plastic product (1) according to any one of claims 1 to 3, which does not comprise one or more of:

5. 5. The three-dimensional plastic product (1) according to any one of claims 1 to 4, wherein the further ingredients are selected from the group consisting of rheology modifiers, foam control agents, luminescent agents, UV-absorbers, plasticizers, reinforcing fibers, preservatives, dyes, curing initiators, organic pigments, inorganic pigments (other than metallic pigment flakes and pearlescent pigment flakes), and combinations thereof.

6. The metallic pigment flakes and the pearlescent pigment flakes are (I) Metal oxides, metals, metal sulfides, titanium suboxide, titanium oxynitride, FeO(OH), SiO ２ , B ２ O ３ , GeO ２ , MgF ２ , metal pigment flakes or mica pigment flakes optionally coated with at least one layer of one or more components selected from the group consisting of metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and a binder; (II) Metal oxides, metals, metal sulfides, titanium suboxide, titanium oxynitride, FeO(OH), SiO ２ , B ２ O ３ , GeO ２ Al coated with at least one layer of one or more components selected from the group consisting of metal alloys and rare earth compounds. ２ O ３ , SiO ２ , pigment flakes comprising glass, ceramic, graphite or mica platelets, optionally coated with an outer layer comprising one or more colorants and a binder; (III) TiO ２ , ZrO ２ , SiO ２ , SnO ２ , In ２ O ３ Al doped with one or more components selected from the group consisting of ZnO and iron oxide ２ O ３ Platelets include metal oxides, metals, metal sulfides, titanium suboxide, titanium oxynitride, FeO(OH), SiO ２ , B ２ O ３ , GeO ２ , metal alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and a binder. The three-dimensional plastic product (1) according to any one of claims 1 to 5, selected from the group consisting of:

7. A three-dimensional plastic product (1) according to any one of the preceding claims, wherein said spherical glass beads have a refractive index measured at a wavelength λ of 589 nm of between 2.0 and 2.6, preferably between 2.1 and 2.

4.

8. 8. The three-dimensional plastic product (1) according to any one of claims 1 to 7, comprising a thermoplastic polymer selected from the group consisting of polyethylene homopolymers and copolymers (PE, LDPE, HDPE, LLDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide (PA), polyoxymethylene (POM), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polysulfone (PSU), polyimide (PI), polybutene (PB), polyether ether ketone (PEEK), poly(acrylonitrile butadiene styrene) (ABS), poly(acrylonitrile butadiene acrylate) (ABA), poly(acrylstyrene acrylonitrile) (ASA), polylactic acid (PLA), nylon and blends thereof.

9. The three-dimensional plastic product (1) according to any one of claims 1 to 7, comprising a thermosetting polymer, said thermosetting polymer being selected from the group consisting of phenol formaldehyde (PF), urea formaldehyde (UF), melamine formaldehyde (MF), epoxy (EP), polyurethane (PU) and unsaturated polyester (UP).

10. A three-dimensional plastic product (1) according to any one of claims 1 to 8, in the form of filaments or pellets, said polymer being a thermoplastic polymer.

11. One or more three-dimensional plastic products (1) according to any one of claims 1 to 10 and one or more further parts or components (3) attached thereto, or A modified three-dimensional product (2) comprising one or more further parts or components (3) and one or more three-dimensional plastic products (1) according to any one of claims 1 to 10 attached thereto, However, a modified three-dimensional product (2) in which at least a portion of one or more outer retroreflective surface portions (C) of the three-dimensional plastic product (1) according to the first aspect is not covered by the one or more further parts or components (3).

12. A method for producing a three-dimensional plastic product (1) with retroreflective properties according to any one of claims 1 to 8 and 10, wherein the polymer is a thermoplastic polymer, said method comprising: (a) providing the thermoplastic polymer, the spherical glass beads, the pigment flakes, and the optional additional ingredients; (b) blending the components provided in step (a) at a temperature above the melting point of the thermoplastic polymer; (c) feeding the mixture obtained in step (b) into a die or extruding the mixture obtained in step (b); (d) cooling the mixture in the mold to a temperature below the melting point of the thermoplastic polymer and removing the three-dimensional plastic article (1) with retroreflective properties from the mold, or cooling the extrudate to a temperature below the melting point of the thermoplastic polymer to provide a three-dimensional plastic article (1) with retroreflective properties.

13. A method for producing a three-dimensional plastic product (1) with retroreflective properties according to any one of claims 1 to 7 and 9, wherein the polymer is a thermosetting polymer, said method comprising: (a) providing a thermosetting resin, the spherical glass beads, the pigment flakes, and the optional additional ingredients; (b) mixing the ingredients provided in step (a); (c) feeding the mixture obtained in step (b) into a mold; (d) curing the mixture in the mold to provide said three-dimensional plastic article (1) with retroreflective properties; (e) removing said three-dimensional plastic article (1) with retroreflective properties from the mold.

14. A laser imaging detection and ranging (LIDAR) method for a three-dimensional plastic product (1) according to any one of claims 1 to 10 or a modified three-dimensional product (2) according to claim 11, comprising: (i) providing a LIDAR device comprising an electromagnetic radiation source, a receiver and optionally a Global Positioning System (GPS); (ii) transmitting electromagnetic radiation from the electromagnetic radiation source of the LIDAR device to the three-dimensional plastic product (1) or the modified three-dimensional product (2); (iii) scanning the electromagnetic radiation reflected by the three-dimensional plastic product (1) or the modified three-dimensional product (2) with the receiver of the LIDAR device; (iv) from the difference between the transmitted electromagnetic radiation and the scanned reflected electromagnetic radiation, preferably as a function of time; the distance between the three-dimensional plastic product (1) or the modified three-dimensional product (2) and the LIDAR device; the acceleration of the three-dimensional plastic product (1) or the modified three-dimensional product (2); the deceleration of the three-dimensional plastic product (1) or the modified three-dimensional product (2), the direction of movement of the three-dimensional plastic product (1) or the modified three-dimensional product (2); the velocity of the three-dimensional plastic product (1) or the modified three-dimensional product (2), preferably relative to the velocity of the LIDAR device, and a 3D image of said three-dimensional plastic product (1) or said modified three-dimensional product (2); and computing one or more of:

15. Use of a three-dimensional plastic product (1) in the form of a filament or pellet according to claim 10 in the production of a ready-to-use three-dimensional plastic product (1) according to any one of claims 1 to 8, wherein the polymer is a thermoplastic polymer.

16. A three-dimensional plastic product (1) according to any one of claims 1 to 10 or a modified three-dimensional product (2) according to claim 11, in laser imaging detection and ranging (LIDAR) of the three-dimensional plastic product (1) or the modified three-dimensional product (2), and / or to improve the visibility of the three-dimensional plastic product (1) or the modified three-dimensional product (2) under visible light conditions, and / or Use for preparing a three-dimensional image of said three-dimensional plastic product (1) or said modified three-dimensional product (2).

Images