Method for Providing Organic Solvent-Based Compositions Having Retroreflective Properties - Patent application

Abstract

The present invention relates to a method for providing a composition selected from the group consisting of organic solvent-based paste, ink, paint, and coating formulations having retroreflective properties, the method comprising the steps of: a) providing an organic solvent-based paste, ink, paint, or coating formulation without retroreflective properties; b) providing a retroreflective organic solvent-based composition; and c) mixing the organic solvent-based ink, paint, or coating formulation without retroreflective properties provided in step (a) with the retroreflective organic solvent-based composition provided in step (b) in a weight ratio of between 30:70 and 70:30 to provide an organic solvent-based paste, ink, paint, or coating formulation with retroreflective properties.

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to a method for providing a composition selected from the group consisting of organic solvent-based paste, ink, paint and coating formulations having retroreflective properties. The present invention relates to said method further comprising the step of applying the retroreflective composition to a substrate. Background of the Invention

[0002] Retroreflective effects are used in a variety of applications, such as to improve the visibility of road signs, road markers, fabrics, automobiles, etc. under dark conditions, or simply to improve their visual appearance. Road markers are typically given retroreflective properties by the addition of spherical glass beads with a specific refractive index. Retroreflection occurs through the tandem action of refraction of incident light through the top surface of the spherical glass beads, internal reflection from the lower inner surface of the spherical glass beads, and then refraction of light as it exits the top surface of the spherical glass beads back in the direction from which it came.

[0003] WO 2004 / 017104 discloses a retroreflective composition comprising retroreflective microspheres, a binder system, and a thixotropic blend comprising at least two thixotropic agents in an amount of about 2 to about 5% by weight based on the retroreflective composition. The retroreflective compositions are intended for use as paints, inks, and coatings and are applied to substrates using an aerosol applicator with a propellant.

[0004] WO 00 / 42113 relates to retroreflective inks comprising microbeads in a liquid carrier medium. The inks are intended for screen printing onto fabrics.

[0005] Organic solvent-based paste, paint, ink and coating formulations are commercially offered by many suppliers in different colors and / or tailored for different applications. Every new application and every modification of an organic solvent-based paste, paint, ink or coating formulation requires a costly and time-consuming development process from laboratory samples to commercial products. Obviously, offering many products in different colors and / or for different applications requires large warehouses and large inventories that can quickly respond to customer orders.

[0006] As explained above, adding retroreflective properties to paste, paint, ink and coating formulations can be advantageous as it results in improved visibility and / or a more attractive visual appearance.

[0007] Because the addition of additional ingredients, including retroreflective spherical glass beads, should not substantially affect the processability of existing paste, paint, ink or coating formulations, let alone the properties of the paste, paint, ink or coating formulation after drying or curing, the development of retroreflective versions of already commercially available organic solvent-based paste, paint, ink and coating formulations also requires a costly and time-consuming development process. Large warehouses are even required to offer retroreflective paste, paint, ink and coating formulations in addition to paste, paint, ink and coating formulations without retroreflective properties.

[0008] Therefore, there is a need for an efficient method for providing on demand, i.e., commercially available, organic solvent based paste, paint, ink and coating formulations with retroreflective properties without substantially changing the processability of the organic solvent based paint, ink and coating formulations and without substantially affecting the properties of the paste, paint, ink or coating formulation after drying or curing.

[0009] As shown in the accompanying examples, the inventors have determined that providing organic solvent based paste, paint, ink and coating formulations with retroreflective properties cannot be achieved by simply mixing an organic solvent based paste, paint, ink or coating formulation with retroreflective spherical glass beads, as this results in inhomogeneity, air entrapment and / or instability in the distribution of the spherical glass beads throughout the composition.

[0010] It is therefore an object of the present invention to provide an efficient method for providing organic solvent based paste, paint, ink and coating formulations with retroreflective properties without substantially altering the processability of the organic solvent based paste paint, ink and coating formulations and / or without adversely affecting the properties of the paste, paint, ink or coating formulation after drying or curing.

[0011] It is a further object of the present invention to provide an efficient method for providing organic solvent based paste, paint, ink and coating formulations containing retroreflective spherical glass beads that results in a homogenous and stable distribution of the retroreflective spherical glass beads throughout the composition.

[0012] [Summary of the invention] The inventors have unexpectedly determined that one or more objectives can be met by mixing an organic solvent based paste, paint, ink or coating formulation lacking retroreflective properties with an organic solvent based composition comprising retroreflective spherical glass beads and thickener(s), said organic solvent based composition having a first Brookfield viscosity η2 at a shear rate of 0.5 rpm between 5 and 350 Pa·s, and a second Brookfield viscosity η3 at a shear rate of 20 rpm between 100 and 5000 mPa·s, where η2 and η3 are measured using a #4 spindle at a temperature of 20° C., and where η3 is at least two times lower than η2, and optionally subsequently adding additional thickener.

[0013] Thus, in a first aspect, the present invention provides a method for providing a composition selected from the group consisting of organic solvent-based paste, ink, paint and coating formulations having retroreflective properties, comprising the steps of: a) From 1 mPa s measured using a #1 spindle in a 600 ml beaker with a diameter of 8.25 cm providing an organic solvent based paste, ink, paint or coating formulation without retroreflective properties, having a Brookfield viscosity η1 at a shear rate of 0.5 rpm and a temperature of 20° C. of between 300 Pa·s as measured with a #5 spindle in a 600 ml beaker having a diameter of 8.25 cm; b) providing a retroreflective organic solvent-based composition having a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm at a temperature of 20° C. using a #4 spindle, at a shear rate of 0.5 rpm, between 5 and 350 Pa s, and at a shear rate of 20 rpm, between 100 and 5000 mPa s, where η3 is at least two times lower than η2; The retroreflective organic solvent-based composition comprises, based on the total weight of the retroreflective organic solvent-based composition 10-49.85% by weight of organic solvent; 50-85% by weight of spherical glass beads having a median particle size D50 between 1 and 1500 μm as measured using laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; 0.15 to 3.5% by weight of a thickening agent; and 0-10% by weight of one or more further ingredients; c) mixing the organic solvent-based ink, paint or coating formulation without retroreflective properties provided in step (a) with the retroreflective organic solvent-based composition provided in step (b) in a weight ratio of between 30:70 and 70:30 to provide an organic solvent-based paste, ink, paint or coating formulation having retroreflective properties; d) optionally mixing the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) with 0-4.5% by weight of synthetic pigment flakes having an average diameter between 5 and 150 μm, a thickness of less than 1 μm and an aspect ratio of at least 10, based on the total weight of the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c); and e) optionally mixing the mixture obtained in step (c) or (d) with 0 to 3 wt. % of a thickener, based on the total weight of the organic solvent based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) or (d), respectively.

[0014] The retroreflective organic solvent-based composition prepared in step (b) consists mainly of organic solvent and spherical glass beads. The inert spherical glass beads have no or little effect on organic solvent-based paste, ink, paint or coating formulations. Therefore, these systems are very compatible with "commercial" organic solvent-based paste, ink, paint or coating formulations. The organic solvent disappears from the paste, ink, paint or coating formulation upon drying or curing. The inventors have established that the processability of the organic solvent-based paste, paint, ink and coating formulations prepared in step (a) is not significantly altered when the retroreflective organic solvent-based composition defined in step (b) is added in appropriate amounts together with the optional addition of a thickener. Because the retroreflective spherical glass beads are added in the form of a sufficiently stable, homogeneous organic solvent-based composition as defined in step (b), they can be added without air entrainment to an organic solvent-based paste, ink, paint or coating formulation lacking retroreflective properties as defined in step (a), resulting in a sufficiently stable, homogeneous organic solvent-based paste, ink, paint or coating formulation that has retroreflective properties.

[0015] definition The term "shear thinning behavior" in the context of the retroreflective organic solvent-based composition provided in step (b) of the process defined herein relates to the decrease in viscosity when the composition, initially in a static state, is subjected to a shear rate.

[0016] Detailed Description In a first aspect, the present invention provides a method for providing a composition selected from the group consisting of organic solvent-based paste, ink, paint and coating formulations having retroreflective properties, comprising the steps of: a) From 1 mPa s measured using a #1 spindle in a 600 ml beaker with a diameter of 8.25 cm providing an organic solvent based paste, ink, paint or coating formulation without retroreflective properties, having a Brookfield viscosity η1 at a shear rate of 0.5 rpm and a temperature of 20° C. of between 300 Pa·s as measured with a #5 spindle in a 600 ml beaker having a diameter of 8.25 cm; b) providing a retroreflective organic solvent-based composition having a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm at a temperature of 20° C. using a #4 spindle, at a shear rate of 0.5 rpm, between 5 and 350 Pa s, and at a shear rate of 20 rpm, between 100 and 5000 mPa s, where η3 is at least two times lower than η2; The retroreflective organic solvent-based composition comprises, based on the total weight of the retroreflective organic solvent-based composition 10-49.85% by weight of organic solvent; 50-85% by weight of spherical glass beads having a median particle size D50 between 1 and 1500 μm as measured using laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; 0.15 to 3.5% by weight of a thickening agent; and 0-10% by weight of one or more further ingredients; c) mixing the organic solvent-based ink, paint or coating formulation without retroreflective properties provided in step (a) with the retroreflective organic solvent-based composition provided in step (b) in a weight ratio of between 30:70 and 70:30 to provide an organic solvent-based paste, ink, paint or coating formulation having retroreflective properties; d) optionally mixing the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) with 0-4.5% by weight of synthetic pigment flakes having an average diameter between 5 and 150 μm, a thickness of less than 1 μm and an aspect ratio of at least 10, based on the total weight of the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c); and e) optionally mixing the mixture obtained in step (c) or (d) with 0 to 3 wt. % of a thickener, based on the total weight of the organic solvent based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) or (d), respectively.

[0017] In a highly preferred embodiment, a first aspect is a method for providing a composition selected from the group consisting of organic solvent based paste, ink, paint and coating formulations having retroreflective properties, comprising the steps of: a) From 1 mPa s measured using a #1 spindle in a 600 ml beaker with a diameter of 8.25 cm providing an organic solvent based paste, ink, paint or coating formulation without retroreflective properties, having a Brookfield viscosity η1 at a shear rate of 0.5 rpm and a temperature of 20° C. of between 300 Pa·s as measured with a #5 spindle in a 600 ml beaker having a diameter of 8.25 cm; b) providing a retroreflective organic solvent-based composition having a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm at a temperature of 20° C. using a #4 spindle, at a shear rate of 0.5 rpm, between 5 and 350 Pa s, and at a shear rate of 20 rpm, between 100 and 5000 mPa s, where η3 is at least two times lower than η2; The retroreflective organic solvent-based composition comprises, based on the total weight of the retroreflective organic solvent-based composition 15-49.85 wt.% organic solvent; 50-80% by weight of spherical glass beads having a median particle size D50 between 1 and 1500 μm as measured using laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; 0.15 to 3.5% by weight of a thickening agent; and 0-10% by weight of one or more further ingredients; c) mixing the organic solvent-based ink, paint or coating formulation without retroreflective properties provided in step (a) with the retroreflective organic solvent-based composition provided in step (b) in a weight ratio of between 30:70 and 70:30 to provide an organic solvent-based paste, ink, paint or coating formulation having retroreflective properties; d) optionally mixing the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) with 0-4.5% by weight of synthetic pigment flakes having an average diameter between 5 and 150 μm, a thickness of less than 1 μm and an aspect ratio of at least 10, based on the total weight of the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c); and e) optionally mixing the mixture obtained in step (c) or (d) with 0 to 3 wt. % of a thickener, based on the total weight of the organic solvent based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) or (d), respectively.

[0018] As will be appreciated by those skilled in the art, limited settling, (phase) separation and / or syneresis of the retroreflective organic solvent-based compositions prepared in step (b) of the process defined herein is not an issue if said compositions can be resuspended to obtain compositions that remain homogeneous for a long enough time to process them, for example using simple agitation (i.e., by mixing them with the organic solvent-based paste, ink, paint or coating formulations without retroreflective properties prepared in step (a) of the process defined herein). Similarly, limited settling, (phase) separation and / or syneresis of the organic solvent-based paste, ink, paint or coating formulations with retroreflective properties prepared in steps (c), (d) or (e) of the process defined herein is not an issue if said compositions can be resuspended to obtain compositions that remain stable and homogeneous for a long enough time to process them, for example using simple agitation (i.e., by applying them to the substrate of interest). As shown in the accompanying examples, both the retroreflective organic solvent-based compositions prepared in step (b) of the process defined herein, and the organic solvent-based paste, ink, paint or coating formulations having retroreflective properties prepared in steps (c), (d) or (e) of the process defined herein, remain stable and homogeneous for a time long enough to permit their processing.

[0019] In step (c), the organic solvent based paste, ink, paint or coating formulation provided in step (a) is mixed with the retroreflective organic solvent based composition provided in step (b) preferably in a weight ratio of between 60:40 and 40:60, more preferably between 45:55 and 55:45.

[0020] In a preferred embodiment, the method defined herein further comprises the step of applying the organic solvent based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c), (d) or (e) to a substrate using screen printing, curtain coating, mist coating or spray painting.

[0021] In a preferred embodiment, steps (c), (d) and (e) are performed with stirring at a temperature between 15 and 30° C. Stirring is preferably performed at a low shear rate to avoid the incorporation of air bubbles. In another preferred embodiment, step (c) comprises adding the retroreflective organic solvent-based composition provided in step (b) to the non-retroreflective organic solvent-based paste, ink, paint or coating formulation provided in step (a).

[0022] The synthetic pigment flakes added in optional step (d) are preferably selected from the synthetic pigment flakes defined herein under "Additional Ingredients".

[0023] Organic solvents The term "organic solvent" as used herein relates to an organic solvent or mixture of organic solvents containing less than 3% by weight water, preferably less than 2% by weight water, more preferably less than 1% by weight water, even more preferably less than 0.5% by weight water (most preferably anhydrous).

[0024] Preferred organic solvents are selected from the group consisting of aliphatic and aromatic solvents, ketones, esters, glycoethers, alcohols, halogenated hydrocarbons, and combinations thereof.Highly preferred organic solvents are selected from the group consisting of xylene (mixture of isomers), toluene, ethylbenzene, naphtha, 1,2,4-trimethylbenzene, mesitylene, n-propylbenzene, isopentyl acetate, n-butyl acetate, (2-methoxymethylethoxy)propanol, 2-butoxyethyl acetate, 2-methylbutyl acetate, isobutanol, 1-butanol, 1-ethoxypropan-2-ol, 2,6-dimethyl-4-heptanone, 2-methoxy-1-methylethyl acetate, 4,6-dimethyl-heptan-2-one, 4-methyl-2-pentanone, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, 2-(2-butoxyethoxy)ethanol, 2-butoxyethanol, 5-methylhexan-2-one, ethyl acetate, and combinations thereof.

[0025] In a highly preferred embodiment, the amount of organic solvent is from 15 to 49.85 weight percent, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0026] In a preferred embodiment, the amount of organic solvent is 20-45 wt %, more preferably 25-40 wt %, and even more preferably 28-35 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0027] In embodiments, the amount of organic solvent is 15-48 wt%, 15-45 wt%, 15-42 wt%, 15-40 wt%, or 15-38 wt%, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0028] In embodiments, the amount of organic solvent is 10-48 wt%, 10-45 wt%, 10-42 wt%, 10-40 wt%, or 10-38 wt%, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0029] In other embodiments, the amount of organic solvent is 20-49.85 wt%, 24-49.85 wt%, 26-49.85 wt%, 28-49.85 wt%, 29-49.85 wt%, or 30-49.85 wt%, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0030] Spherical Glass Beads As defined above, the refractive index of the spherical glass beads measured at a wavelength λ of 589 nm lies between 1.5 and 2.8.

[0031] In a preferred embodiment, the spherical glass beads are (a) between 2.0 and 2.8, preferably between 2.1 and 2.4; or (b) a refractive index, measured at a wavelength λ of 589 nm, between 1.7 and 2.1, preferably between 1.8 and 2.0;

[0032] In a preferred embodiment, the term "glass" in "spherical glass beads" as used herein refers to an amorphous, non-crystalline solid and transparent material made of oxides. In another embodiment, the term "glass" in "spherical glass beads" refers to a solid and 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, the density is approximately an additive function of its composition. The density of spherical glass beads with a refractive index between 1.5 and 2.8 is typically between 2.5 and 4.5 g / cm. 3 The value fluctuates between .

[0033] Oxides which 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. The spherical glass beads may contain various combinations of, for example, silica (SiO2), boron oxide (BO3), phosphorus pentoxide (PO5), vanadium pentoxide (VO5), arsenic trioxide (As2O3), germanium oxide (GeO2), calcium oxide (CaO), sodium oxide (Na2O), magnesium oxide (MgO), zinc oxide (ZnO), aluminum oxide (Al2O3), potassium oxide (KO), iron oxide (Fe2O3), lead oxide (PbO), barium oxide (BaO), barium titanate (BaTiO3), titanium oxide (TiO2), lithium oxide (Li2O), strontium oxide (SrO), lanthanum oxide (La2O3), and zirconium oxide (ZrO2). Silica and boron oxide generally have the lowest density. Glasses containing a large weight percentage of these oxides therefore generally result in glass beads with a low refractive index. The refractive index can be increased by the addition of oxides having a high molecular weight. Preferably, the spherical glass beads do not contain PbO.

[0034] Glass beads having a refractive index in the range of 1.5 to 2.51 and their composition in terms of oxides are disclosed in WO 2014 / 109564, which is incorporated herein by reference in its entirety. PbO-free transparent glass beads having a refractive index greater than 2.15 are disclosed in U.S. Pat. No. 4,082,427, which is incorporated herein by reference in its entirety.

[0035] The spherical glass beads may be colored spherical glass beads as long as they maintain transparency. Both colored spherical glass beads made of colored transparent glass and spherical glass beads with a concentric transparent colored coating are included in the present invention. The color may be a natural color brought about by the composition of oxides, or may be intentionally selected by adding a component with a specific color. Colored glass beads with high refractive index and high transparency are disclosed in WO2014 / 109564.

[0036] Thus, in embodiments, at least some of the spherical glass beads are made of a colored transparent glass and / or at least some of the spherical glass beads are coated with a concentric transparent colored coating.

[0037] The spherical glass beads have a median diameter D50 as measured by laser diffraction. The median diameter D50 is therefore the volume median based on the volume distribution. The median diameter D50 is the diameter below which half of the population of spherical glass beads falls. This volume median diameter is often referred to in the art as Dv50 or D v0.5 It is called.

[0038] In a highly preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, of between 5 and 1500 μm.

[0039] In an embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 25 and 100 μm, preferably between 30 and 75 μm, more preferably between 35 and 50 μm.

[0040] In a preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, of between 5 and 100 μm, for example between 5 and 75 μm, between 5 and 50 μm, between 5 and 45 μm, between 5 and 40 μm or between 5 and 35 μm.

[0041] In a preferred embodiment, the spherical glass beads have a median particle size D50 measured using laser diffraction of between 1 and 100 μm, for example between 1 and 75 μm, between 1 and 50 μm, between 1 and 45 μm, between 1 and 40 μm, between 1 and 35 μm, between 1 and 30 μm, between 1 and 25 μm, between 1 and 20 μm, between 1 and 15 μm, or between 1 and 10 μm.

[0042] In yet another embodiment, the spherical glass beads have a median particle size D50, as measured using laser diffraction, between 25 and 150 μm, e.g., between 50 and 150 μm, between 75 and 150 μm, between 100 and 150 μm, between 110 and 150 μm, or between 115 and 150 μm.

[0043] In yet another embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 5 and 1400 μm, e.g., between 5 and 1200 μm, between 5 and 1000 μm, between 5 and 800 μm, between 5 and 500 μm, or between 5 and 300 μm.

[0044] In yet another embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 1 and 1400 μm, e.g., between 1 and 1200 μm, between 1 and 1000 μm, between 1 and 800 μm, between 1 and 500 μm, or between 1 and 300 μm.

[0045] The diameters D10 and D90 are often referred to in the art as Dv10 or D v0.1 and Dv90 or D v0.9 The D10 diameter is the diameter below which 10% of a population of spherical glass beads fall. Similarly, the D90 diameter is the diameter below which 90% of a population of spherical glass beads fall.

[0046] The span of the particle size distribution of spherical glass beads as measured by laser diffraction is defined as follows:

[0047]

number

[0048] In another embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 15 and 100 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0049] In yet another embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 30 and 75 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0050] In another preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 15 and 50 μm and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2 or between 0 and 0.1.

[0051] In yet another preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 5 and 35 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0052] In yet another preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 1 and 35 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0053] In yet another preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 10 and 25 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0054] In yet another preferred embodiment, the spherical glass beads have a median particle size D50 measured using laser diffraction between 1 and 25 μm and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0055] In yet another preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 1 and 15 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0056] In yet another preferred embodiment, the spherical glass beads have a median particle size D50, measured using laser diffraction, between 1 and 10 μm, and a span between 0 and 1.9, such as between 0 and 1.5, between 0 and 1, between 0 and 0.5, between 0 and 0.2, or between 0 and 0.1.

[0057] As will be appreciated by those skilled in the art, span=0 corresponds to monodisperse spherical glass beads.

[0058] In a preferred embodiment, at least a portion of the spherical glass beads are hemispherically coated with a light reflective coating, preferably with a hemispherical aluminum coating (HAC). In another embodiment, at least a portion of the spherical glass beads are fluorochemically coated.

[0059] The particular application of the organic solvent-based ink, coating or paint composition having retroreflective properties prepared in step (c), (d) or (e) will determine the optimum refractive index of the spherical glass beads used in the retroreflective organic solvent-based composition prepared in step (b). When the composition is applied in a dry environment or onto a substrate that will exhibit retroreflectivity under dry conditions, and when the applied layer of retroreflective spherical glass beads is not coated with an additional layer, the refractive index of the spherical glass beads, measured at a wavelength λ of 589 nm, may be between 1.8 and 2.8.

[0060] In an embodiment, the retroreflective organic solvent-based composition provided in step (b) and the organic solvent-based ink, coating or paint composition having retroreflective properties provided in steps (c), (d) or (e) comprise spherical glass beads having a refractive index, measured at a wavelength λ of 589 nm, of between 1.8 and 2.0.

[0061] On the other hand, if the composition is to be applied in a wet environment or on a substrate that will exhibit retroreflectivity under wet conditions, or if the applied layer of retroreflective spherical glass beads is coated with one or more additional transparent layers, the refractive index of the spherical glass beads measured at a wavelength λ of 589 nm is preferably between 2.0 and 2.8, more preferably between 2.2 and 2.4. Compositions that will exhibit retroreflectivity under both dry and wet conditions, and if the applied layer of retroreflective spherical glass beads is coated with one or more additional transparent layers or is uncoated, can include different types of glass beads having different refractive indices and, optionally, different sizes. In an embodiment, the retroreflective organic solvent-based composition provided in step (b) and the organic solvent-based ink, coating or paint composition having retroreflective properties provided in steps (c), (d) or (e) include spherical glass beads having a refractive index measured at a wavelength λ of 589 nm between 2.0 and 2.8, preferably between 2.2 and 2.4.

[0062] In another embodiment, the retroreflective organic solvent-based composition provided in step (b) and the organic solvent-based ink, coating, or paint composition having retroreflective properties provided in steps (c), (d), or (e) comprise at least two types of spherical glass beads, at least one type of spherical glass beads having a refractive index, measured at a wavelength λ of 589 nm, of between 1.8 and less than 2.0, and at least one further type of spherical glass beads having a refractive index, measured at a wavelength λ of 589 nm, of between 2.0 and 2.8.

[0063] In a highly preferred embodiment, the amount of spherical glass beads is 50 to 80 weight percent, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0064] In a preferred embodiment, the amount of spherical glass beads is 53 to 75 wt %, more preferably 58 to 72 wt %, and even more preferably 60 to 70 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0065] In embodiments, the amount of spherical glass beads is 50-78 wt%, 50-75 wt%, 50-73 wt%, 50-72 wt%, 50-71 wt%, 50-70 wt%, or 50-69 wt%, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0066] In other embodiments, the amount of spherical glass beads is 52-80%, 54-80%, 56-80%, 57-80%, 58-80%, 59-80%, or 60-80% by weight, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0067] In still other embodiments, the amount of spherical glass beads is 52-85%, 54-85%, 56-85%, 57-85%, 58-85%, 59-85%, or 60-85% by weight, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0068] Thickener The retroreflective organic solvent-based composition provided in step (b) of the method defined herein includes a thickener. This may (optionally) be the same thickener applied in step (e). The term thickener as used herein may also refer to a combination of one or more thickeners. Thus, thickener and thickeners are both used and have the same meaning unless otherwise indicated.

[0069] In an embodiment, a single thickening agent is used in the retroreflective organic solvent-based composition provided in step (b), hi another embodiment, a single thickening agent is used in step (e).

[0070] In a preferred embodiment, the thickening agent comprises a mixture of different thickening agents. In an embodiment, a mixture of different thickening agents is used in the retroreflective organic solvent-based composition provided in step (b). In another embodiment, a mixture of different thickening agents is used in step (e).

[0071] In embodiments, the thickener applied in step (e) is the same thickener applied in the retroreflective organic solvent-based composition provided in step (b). In other embodiments, the thickener applied in step (e) is different from the thickener applied in the retroreflective organic solvent-based composition provided in step (b).

[0072] As will be appreciated by those skilled in the art, the non-retroreflective organic solvent based paste, ink, paint or coating formulation provided in step (a) may also include a thickener, which, if present, may be the same as or different from the thickener applied in step (b) and / or the thickener applied in step (e).

[0073] Without wishing to be bound by any theory, it is believed that the thickening agent limits or reduces settling and / or sedimentation of the spherical glass beads and optionally further particulate matter in the retroreflective organic solvent-based composition provided in step (b) and the final organic solvent-based paste, ink, paint or coating formulation having retroreflective properties provided in steps (c), (d) or (e), such that these compositions can be easily resuspended. Further, without wishing to be bound by any theory, it is believed that the thickening agent provides the retroreflective organic solvent-based composition provided in step (b) with shear thinning behavior.

[0074] In a preferred embodiment, the amount of thickener in the retroreflective organic solvent-based composition prepared in step (b) is 0.20 to 3.0 wt %, more preferably 0.25 to 2.5 wt %, and even more preferably 0.30 to 2.1 wt %, based on the total weight of the retroreflective organic solvent-based composition prepared in step (b).

[0075] In an embodiment, the amount of thickener in the retroreflective organic solvent-based composition provided in step (b) is 0.15 to 2.5 wt %, 0.15 to 2.0 wt %, 0.15 to 1.75 wt %, 0.15 to 1.5 wt %, or 0.15 to 1.3 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0076] In other embodiments, the amount of thickener in the retroreflective organic solvent-based composition provided in step (b) is 0.20-3.50 wt %, 0.30-3.50 wt %, 0.40-3.50 wt %, 0.50-3.50 wt %, 0.60-3.50 wt %, 0.70-3.50 wt %, or 0.80-3.50 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0077] In a preferred embodiment, the mixture obtained in step (c) or (d) is mixed in step (e) with 0-2.5 wt%, 0-2.0 wt%, 0-1.8 wt%, 0-1.6 wt%, 0-1.5 wt%, 0-1.4 wt%, or 0-1.3 wt% of a thickener, based on the total weight of the organic solvent based paste, ink, paint, or coating formulation with retroreflective properties obtained in step (c) or (d), respectively.

[0078] In another preferred embodiment, the mixture obtained in step (c) or (d) is mixed in step (e) with 0.1-3.0 wt%, 0.2-3.0 wt%, 0.3-3.0 wt%, 0.4-3.0 wt%, or 0.5-3.0 wt% of a thickener, based on the total weight of the organic solvent based paste, ink, paint, or coating formulation having retroreflective properties obtained in step (c) or (d), respectively.

[0079] Preferred examples of thickeners that can be used in the retroreflective organic solvent-based compositions provided in step (b) and / or step (e) are selected from the group consisting of (modified) hydrogenated castor oil, clays, modified clays, calcium sulfonate complexes, organophilic phyllosilicates, silica gels, synthetic amorphous silicas, acrylic acid type gelling agents, modified cellulosic materials, polyurea dispersions, solutions of urea modified polyamides, polyurethane dispersions, and combinations thereof.

[0080] Examples of modified clays include BENTONE® LT and BENTONE® 38 (Elementis Global). Examples of silica gels include HDK® N20 (Wacker Chemical Corporation) and AEROSIL® (Evonik). An example of an organophilic phyllosilicate is Claytone 40 (Byk). An example of a modified hydrogenated castor oil is Efka® RM 1900 (BASF). An example of a hydrogenated castor oil is Efka® RM 1920 (BASF). An example of a solution of a urea modified non-polar polyamide in isobutanol / monophenyl glycol is Rheobyk-431 (Byk). An example of a solution of a medium polar urea modified polyamide in isobutanol / solvent naphtha is Rheobyk-430 (Byk). An example of a synthetic amorphous silica is Zeothix® 95 (Huber).

[0081] In a preferred embodiment, in the retroreflective organic solvent-based composition provided in step (b) and / or step (e), two thickeners are preferably present, more preferably: Organophilic phyllosilicates and modified hydrogenated castor oil; or A calcium sulfonate complex and a polyurea dispersion are used.

[0082] The amount of organic solvent in the retroreflective organic solvent-based composition provided in step (b) is specified independently. If the thickener is applied in the form of a dispersion in a solvent, for example, the amount of thickener defined in the context of step (b) relates to the dry weight of the thickener. If the thickener is applied in the form of a dispersion in a solvent, for example, in step (e), the amount of thickener defined in the context of step (e) relates to the dry weight.

[0083] Further ingredients As described above, the retroreflective organic solvent-based composition provided in step (b) includes 0-10 wt. % of one or more additional components. As will be appreciated by those skilled in the art, the "additional" components are different from the other components defined in the retroreflective organic solvent-based composition provided in step (b). In other words, the additional components do not include spherical glass beads, thickeners, and organic solvents.

[0084] In embodiments, the one or more additional components are selected from the group consisting of foam control agents, preservatives, dyes, cure initiators, luminescent agents such as phosphorescent and fluorescent agents, pigments, UV absorbers, binders and resins.

[0085] Binders and resins suitable for organic solvent-based compositions are generally known to those skilled in the art. The binder or resin may be radiation-curable. If the binder or resin is radiation-curable, the further component may include a curing initiator, such as a photoinitiator or a thermal initiator.

[0086] In embodiments, the one or more additional components does not include any one of a dye, a pigment, a binder, a resin, and a cure initiator.

[0087] In a preferred embodiment, the one or more further components does not include any one of a binder, a resin, and a curing initiator.

[0088] In an embodiment, the retroreflective organic solvent-based composition provided in step (b) comprises, as part of one or more additional components, synthetic pigment flakes having an average diameter between 5 and 150 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, said synthetic pigment flakes being selected from (A), (B), (C), or a combination thereof: (A) metal or synthetic mica flakes 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, B2O3, GeO2, MgF2, alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders; (B) 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, B2O3, GeO2, alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders; (C) Flakes comprising Al2O3 platelets doped with one or more components 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 components selected from the group consisting of metal oxides, metals, metal sulfides, titanium suboxides, titanium oxynitrides, FeO(OH), SiO2, B2O3, GeO2, alloys, rare earth compounds, and optionally coated with an outer layer comprising one or more colorants and binders.

[0089] The term "average diameter" refers to the median particle size D50 in the context of synthetic pigment flakes.

[0090] 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 rather are chemically manufactured pigment flakes or chemically / physically engineered naturally occurring pigment flakes. One advantage of using synthetic pigment flakes is that they have a very smooth surface, which can result in increased reflectivity.

[0091] The term "flake" or "platelet" as used herein refers to a pigment shape having a large surface area and a small thickness. Typically, flakes or platelets are characterized by their "aspect ratio", which is defined as the largest dimension (i.e., the largest diameter of the surface divided by the smallest dimension (i.e., the thickness)). Synthetic pigment flakes as used herein have an aspect ratio of at least 10, preferably at least 15, and more preferably at least 20.

[0092] In a preferred embodiment, the average diameter of the synthetic flakes is between 6 and 45 μm, more preferably between 7 and 35 μm, even more preferably between 8 and 25 μm, still more preferably between 9 and 20 μm, and most preferably between 10 and 16 μm.

[0093] In a preferred embodiment, the thickness of the synthetic flakes is between 10 nm and 800 nm, more preferably between 15 nm and 600 nm. In another preferred embodiment, the thickness of the synthetic flakes is between 10 and 200 nm, more preferably between 10 and 150 nm, even more preferably between 10 and 100 nm, and even more preferably between 10 and 50 nm.

[0094] In embodiments, the amount of one or more further components in the retroreflective organic solvent-based composition provided in step (b) is 0-8.0 wt %, 0-6.0 wt %, 0-4.0 wt %, 0-3.0 wt %, 0-2.5 wt %, 0-2.0 wt %, 0-1.5 wt %, 0-1.0 wt %, or 0-0.5 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0095] In other embodiments, the amount of one or more additional components in the retroreflective organic solvent-based composition provided in step (b) is 0.01-10 wt %, 0.02-10 wt %, 0.04-10 wt %, 0.08-10 wt %, 0.15-10 wt %, 0.25-10 wt %, 0.35-10 wt %, 0.45-10 wt %, or 0.55-10 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

[0096] The amount of organic solvent in the retroreflective organic solvent-based composition provided in step (b) is specified independently. When the one or more further components are applied in the form of, for example, a solution, suspension or dispersion in a solvent, the amount of the one or more further components defined above relates to the dry weight, i.e., solvent-free weight, of the one or more further components.

[0097] Rheological behavior The viscosity measured and defined herein is the so-called Brookfield viscosity. As known to those skilled in the art, the Brookfield viscosity of different compositions may need to be measured using different standardized spindles. Very low viscosity compositions are usually measured using spindle #1, but high viscosity compositions are usually measured using spindle #5. Medium viscosity compositions may be measured using spindle #2, #3 or #4.

[0098] The viscosity of the non-retroreflective organic solvent based paste, ink, paint or coating formulation prepared in step (a) of the method defined herein can vary from very low to high values, so that the lower end of the Brookfield viscosity range is determined using spindle #1 and the upper end using spindle #5.

[0099] In a preferred embodiment, the organic solvent based paste, ink, paint or coating formulation without retroreflective properties comprises: 5 mPa·s, more preferably 10 mPa·s, measured using a #1 spindle in a 600 ml beaker with a diameter of 8.25 cm It has a Brookfield viscosity η1 at a shear rate of 0.5 rpm and a temperature of 20° C. of between 280 Pa·s, more preferably 250 Pa·s, measured using a #5 spindle in a 600 ml beaker having a diameter of 8.25 cm.

[0100] The retroreflective organic solvent-based composition provided in step (b) of the method defined herein exhibits shear thinning behavior.

[0101] In a preferred embodiment, the retroreflective organic solvent-based composition provided in step (b) has a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm using a #4 spindle at a temperature of 20° C., η2 at a shear rate of 0.5 rpm between 8 and 325 Pa·s, and η3 at a shear rate of 20 rpm between 110 and 4000 mPa·s, provided that η3 is at least 4 times lower than η2.

[0102] In another preferred embodiment, the retroreflective organic solvent-based composition provided in step (b) has a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm using a #4 spindle at a temperature of 20° C., η2 at a shear rate of 0.5 rpm between 10 and 310 Pa·s, and η3 at a shear rate of 20 rpm between 125 and 4000 mPa·s, provided that η3 is at least 5 times lower than η2.

[0103] In another embodiment, the retroreflective organic solvent-based composition provided in step (b) has a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm using a #4 spindle at a temperature of 20° C., η2 at a shear rate of 0.5 rpm between 5 and 350 Pa·s, and η3 at a shear rate of 20 rpm between 100 and 5000 mPa·s, provided that η3 is at least 30, 50, 60, 70, or 80 times lower than η2.

[0104] In another embodiment, the retroreflective organic solvent-based composition provided in step (b) has a first Brookfield viscosity η2 and a second Brookfield viscosity η3, measured in a 600 ml beaker having a diameter of 8.25 cm using a #4 spindle at a temperature of 20° C., η2 at a shear rate of 0.5 rpm between 5 and 25 Pa·s, and η3 at a shear rate of 20 rpm between 100 and 5000 mPa·s, provided that η3 is at least 2, 3, 4, or 5 times lower than η2.

[0105] Process for preparing retroreflective organic solvent-based compositions The retroreflective organic solvent-based composition provided in step (b) can be prepared as follows: Generally speaking, the components of the retroreflective organic solvent-based composition can be added in any order; however, since homogeneous component distribution becomes more difficult in thickened compositions, it is preferred to add the thickener at the end of the process, after at least the spherical glass beads have been added to the organic solvent.

[0106] In an embodiment, the retroreflective organic solvent-based composition provided in step (b) comprises: (i) adding to a container an organic solvent, spherical glass beads as defined above, a thickening agent as defined above and optionally one or more further ingredients as defined above; and (ii) by stirring or homogenizing the mixture obtained in step (i) at a temperature preferably between 15 and 70° C., for a period preferably between 5 and 60 minutes.

[0107] In a preferred embodiment, the thickening agent is added after stirring or homogenizing the mixture of the organic solvent and the spherical glass beads. In another preferred embodiment, the thickening agent is added after stirring or homogenizing the mixture of the organic solvent, the spherical glass beads and any further ingredients. To avoid the inclusion of air bubbles, the stirring or homogenization is preferably performed at a low shear rate.

[0108] Thus, the invention has been described with reference to certain specific embodiments discussed above, it being recognized that these embodiments are susceptible to various modifications and alternative forms known to those skilled in the art.

[0109] Moreover, for the proper understanding of this specification and its claims, it should be understood that the verb "comprise" and its conjugations are used in an open-ended sense to mean that the items following the word are included, but items not specifically mentioned are not excluded. Furthermore, the reference of an element with the indefinite article "a" or "an" does not exclude the possibility that there are more than one of that element, unless the context clearly dictates that there is only one of that element. Thus, the indefinite article "a" or "an" generally means "at least one." EXAMPLES

[0110] Protocol Viscosity Measurement The viscosity was measured using a Brookfield Ametek® DV2T viscometer at a temperature of 20° C. using different standardized spindles (#1, #2, #3, #4 and #5; LV-1, LV-2, LV-3, LV-4 and LV-5, obtained from Brookfield Ametek®) according to the operating instructions. The measurements were carried out in flat-bottomed 600 ml Griffin beakers with a diameter of 8.25 cm and without protective feet. Before measuring the viscosity, the samples were brought to a temperature of 20° C. and homogenized using stirring.

[0111] Example 1 Three retroreflective organic solvent-based compositions (compositions of the process of the present invention provided in step (b)) were prepared by adding the ingredients in the following order to a vessel (3.5 liters) at room temperature (approximately 20° C.) using a Dispermill Orange-line 18 / 186: (1) adding the organic solvent and starting stirring at 500 rpm; (2) adding glass beads while mixing at 500 rpm for at least 5 minutes; (3) adding the first thickener while mixing for at least 5 minutes at 1300 rpm, slowly increasing the rpm to 2000 rpm without introducing air bubbles; (4) Optionally adding additional thickener, followed by stirring at 1800 rpm for at least 45 minutes, and slowly increasing the rpm, if necessary, without introducing air bubbles; and (5) After the final setting of the thickener(s), the next day, stirring the composition for 15 minutes at about 2300 rpm. The amounts of the various ingredients are listed in Table 1. The following ingredients were used:

[0112] Spherical glass beads: "(AA)" microglass beads (RI 2.2), having a refractive index of about 2.2 measured at a wavelength λ of 589 nm, a median particle size D50 of 26.56 μm, a D10 diameter of 19.77 μm and a D90 diameter of 32.41 μm as measured using laser diffraction, and a mass fraction of about 4.5 g / cm 3 These spherical glass beads were obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd. and have a specific gravity of 1.0 to 1.0 mm. These spherical glass beads contain TiO2, BaO, ZnO, and CaO.

[0113] "(BB)" Micro glass beads (RI 2.2, HAC) obtained from Jianxi Sunflex Light Retroreflective Material Co, Ltd., having a refractive index of about 2.2 measured at a wavelength λ of 589 nm, a median particle size D50 of 40.37 μm, a D10 diameter of 37.32 μm and a D90 diameter of 44.11 μm as measured using laser diffraction, and a mass of about 4.5 g / cm 3 Hemispherical aluminum coated glass beads having a specific gravity of 1.05%. These spherical glass beads contain TiO2, BaO, ZnO and CaO.

[0114] Organic solvents Syrox S8000 thinner (Axalta), a mixture of organic solvents, containing 5-methylhexan-2-one, n-butyl acetate, 2,6-dimethylheptan-4-one and 4,6-dimethylheptan-2-one OK Thinner (Gamma, the Netherlands) Mixtures of organic solvents, such as Chromax XB383 standard thinner (Axalta), including xylene, ethylbenzene, naphtha, 1,2,4-trimethylbenzene, mesitylene, n-propylbenzene, isopentyl acetate, n-butyl acetate, 2-methylbutyl acetate, and 4-methyl-2-pentanone

[0115] Thickener Efka® RM1920, hydrogenated castor oil, fine powder, thickener obtained from BASF Claytone 40, an organophilic phyllosilicate from Byk, a thickener

[0116] [Table 1]

[0117] Example 2 The stability of the three retroreflective organic solvent-based compositions shown in Table 1 was determined by visual and tactile inspection to determine whether the samples exhibited settling, syneresis, or separation (phase or otherwise) immediately prior to resuspension, and whether the samples exhibited settling, syneresis, or separation (phase or otherwise) immediately following resuspension of the mixture, and in addition, whether the samples remained stable and homogeneous for a sufficient period of time after resuspension.

[0118] As will be appreciated by those skilled in the art, limited settling, (phase) separation and / or syneresis of the retroreflective organic solvent-based compositions provided in step (b) of the process according to the invention is not a problem if said compositions can be resuspended to obtain compositions that remain stable and homogeneous for a long enough time to process them, for example using simple stirring (i.e., to mix them with the organic solvent-based paste, ink, paint or coating formulations without retroreflective properties provided in step (a) of the process according to the invention).

[0119] Resuspension was accomplished by vigorous mechanical agitation (without introducing air bubbles) for 5 minutes using an overhead stirrer. The results of stability measurements immediately before and after resuspension are listed in Table 2a. Table 2a lists the settling, syneresis and "air bubble / flocculation" values ​​determined according to the classification shown in Table 2b.

[0120] [Table 2a]

[0121] [Table 2b]

[0122] The Brookfield viscosities of the three retroreflective organic solvent-based compositions shown in Table 1 (prepared in step (b) of the process according to the invention) were determined according to the protocol defined above using spindle #4 at 0.5 rpm and 20 rpm. The results are presented in Table 2c. The three retroreflective organic solvent-based compositions exhibit shear thinning behavior.

[0123] [Table 2c]

[0124] Example 3 The three retroreflective organic solvent-based compositions of Example 1 (provided in step (b) of the process according to the invention) were used in the preparation of five different compositions selected from the group consisting of organic solvent-based paste, ink, paint or coating formulations having retroreflective properties.

[0125] The three retroreflective organic solvent-based compositions of Example 1 (prepared in step (b) of the process according to the invention) were mixed with several commercial products without retroreflective properties (prepared in step (a) of the process according to the invention) listed in Table 3. Table 3 shows the viscosities of the commercial products.

[0126] [Table 3]

[0127] If necessary, additional thickening agent (selected from those listed in Example 1) was added.

[0128] Five compositions selected from the group consisting of organic solvent based paste, ink, paint or coating formulations with retroreflective properties were prepared by adding the ingredients in the following order to a 600 ml beaker at room temperature (approximately 20° C.) using a Dispermill Orange-line 18 / 186: (1) adding an organic solvent based paste, ink, paint or coating formulation without retroreflective properties (Table 3) to a beaker and beginning stirring; (2) adding a retroreflective organic solvent-based composition (Table 1) to the beaker, followed by stirring at 700 to 1500 rpm for about 10 minutes; (3) extending the stirring time for an additional 15 minutes at about 1800 rpm per addition of additional thickener; and (4) After the final setting of the thickener, the next day, stirring the composition for 15 minutes at about 1800-2500 rpm.

[0129] Table 4 lists the amounts of various components in the resulting organic solvent-based paste, ink, paint or coating formulations having retroreflective properties (prepared in step (c) or (e) of the process according to the invention).

[0130] [Table 4]

[0131] The stability of five different compositions selected from the group consisting of organic solvent based paste, ink, paint or coating formulations having retroreflective properties (prepared in step (c) or (e) of the process according to the invention) was determined by visual and tactile inspection to determine whether the samples exhibited settling, syneresis or separation (phase or otherwise) immediately prior to resuspension and whether the samples exhibited settling, syneresis or separation (phase or otherwise) immediately following resuspension of the mixture, and further whether the samples remained stable and homogeneous for a sufficiently long period of time following resuspension.

[0132] As will be appreciated by those skilled in the art, limited settling, (phase) separation and / or syneresis of organic solvent based paste, ink, paint or coating formulations with retroreflective properties (prepared in step (c) or (e) of the process according to the invention) is not an issue if said compositions can be resuspended, for example using simple stirring, to obtain compositions that remain stable and homogeneous for a long enough time to process them (i.e. apply them to the target substrate).

[0133] Resuspension was accomplished by vigorous mechanical agitation (without introducing air bubbles) for 5 minutes using an overhead stirrer. The results of stability measurements immediately before and after resuspension are listed in Table 5. Table 5 lists the settling, syneresis and "air bubble / flocculation" values ​​determined according to the classification shown in Table 2b.

[0134] [Table 5]

[0135] Example 4 Five different compositions selected from the group consisting of organic solvent based paste, ink, paint or coating formulations having retroreflective properties as disclosed in Table 4 were applied to the corresponding "Objectives" as disclosed in Table 3 using the corresponding "Methods of Application" as disclosed in Table 3, resulting in visually appealing coated substrates having retroreflective properties.

[0136] Comparative Example Five comparative retroreflective compositions were prepared by directly mixing a composition selected from the group consisting of organic solvent-based paste, ink, paint or coating formulations (as defined in Example 3) with the spherical glass beads as defined in Example 1. The comparative retroreflective compositions were prepared as follows: A commercially available organic solvent-based paste, ink, paint or coating formulation without retroreflective properties was placed in a beaker. The spherical glass beads were then added, followed by thorough mixing for 7-10 minutes at 1000-2100 rpm using a Dispermill Orange-line 18 / 186. The process was carried out at room temperature (approximately 20° C.). The amounts of the various components in the resulting comparative compositions are listed in Table 6.

[0137] [Table 6]

[0138] The stability of the five comparative retroreflective compositions was evaluated seven days after fabrication. Table 7 lists the settling, syneresis and "air bubble / clumping" values ​​of the five comparative retroreflective compositions, determined according to the classification shown in Table 2b. The samples exhibited moderate to severe settling, such that they (samples T01236, T01237 and T01240) could not be resuspended or could hardly be resuspended (T01238 and T01239). Furthermore, sample T01239 exhibited air bubbles and clumping.

[0139] [Table 7]

Claims

1. 1. A method for providing a composition selected from the group consisting of organic solvent based paste, ink, paint and coating formulations having retroreflective properties, comprising: a) From 1 mPa·s measured using a #1 spindle in a 600 ml beaker with a diameter of 8.25 cm Brookfield viscosity η at a shear rate of 0.5 rpm and a temperature of 20° C. between 300 Pa s measured using a #5 spindle in a 600 ml beaker with a diameter of 8.25 cm １ providing an organic solvent based paste, ink, paint or coating formulation without retroreflective properties having: b) First Brookfield viscosity η ２ and the second Brookfield viscosity η ３ is measured using a #4 spindle at a temperature of 20° C. in a 600 ml beaker having a diameter of 8.25 cm, and η ３ η ２ η at a shear rate of 0.5 rpm between 5 and 350 Pa s, provided that the η is at least 2 times lower than ２ , and η between 100 and 5000 mPa·s at a shear rate of 20 rpm ３ providing a retroreflective organic solvent-based composition having The retroreflective organic solvent-based composition comprises, based on the total weight of the retroreflective organic solvent-based composition 10 to 49.85 wt. % of an organic solvent; 50-85% by weight of spherical glass beads having a median particle size D50 between 1 and 1500 μm as measured using laser diffraction and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; 0.15 to 3.5 wt. % of a thickening agent; and 0-10% by weight of one or more further ingredients; c) mixing the non-retroreflective organic solvent-based ink, paint or coating formulation provided in step (a) with the retroreflective organic solvent-based composition provided in step (b) in a weight ratio of between 30:70 and 70:30 to provide an organic solvent-based paste, ink, paint or coating formulation having retroreflective properties; d) optionally mixing the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) with 0-4.5% by weight, based on the total weight of the organic solvent-based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c), of synthetic pigment flakes having an average diameter between 5 and 150 μm, a thickness of less than 1 μm and an aspect ratio of at least 10; and e) optionally mixing the mixture obtained in step (c) or (d) with 0-3 wt. % of a thickener, based on the total weight of the organic solvent based paste, ink, paint or coating formulation having retroreflective properties obtained in step (c) or (d), respectively.

2. The retroreflective organic solvent-based composition provided in step (b) comprises, based on the total weight of the retroreflective organic solvent-based composition, 15 to 49.85 wt. % of an organic solvent; 50-80% by weight of spherical glass beads having a median particle size D50, measured using laser diffraction, between 5 and 1500 μm, and a refractive index, measured at a wavelength λ of 589 nm, between 1.5 and 2.8; 0.15 to 3.5 wt. % of a thickening agent; and The method of claim 1, comprising 0-10% by weight of one or more further ingredients.

3. The retroreflective organic solvent-based composition provided in step (b) has a first Brookfield viscosity η ２ and the second Brookfield viscosity η ３ is measured in a 600 ml beaker having a diameter of 8.25 cm using a #4 spindle at a temperature of 20° C. ３ η ２ η at a shear rate of 0.5 rpm from 8 to 325 Pa s, provided that it is at least 4 times lower than ２ and η between 110 and 4000 mPa·s at a shear rate of 20 rpm ３ 2. The method of claim 1, comprising:

4. The organic solvent-based paste, ink, paint or coating formulation without retroreflective properties provided in step (a) is 5 mPa·s, more preferably 10 mPa·s, measured using a #1 spindle in a 600 ml beaker having a diameter of 8.25 cm. Brookfield viscosity η at a shear rate of 0.5 rpm and a temperature of 20° C. between 280 Pa·s, more preferably 250 Pa·s, measured with a #5 spindle in a 600 ml beaker having a diameter of 8.25 cm １ 2. The method of claim 1, comprising:

5. The spherical glass beads in the retroreflective organic solvent-based composition provided in step (b) are (i) between 2.0 and 2.8, preferably between 2.1 and 2.4; or 2. The method of claim 1, wherein (ii) the refractive index, measured at a wavelength λ of 589 nm, is between 1.7 and 2.1, preferably between 1.8 and 2.

0.

6. 2. The method of claim 1, wherein the spherical glass beads in the retroreflective organic solvent-based composition provided in step (b) have a median particle size D50 measured using laser diffraction of between 1 and 100 μm, between 1 and 75 μm, between 1 and 50 μm, between 1 and 45 μm, between 1 and 40 μm, or between 1 and 35 μm.

7. 2. The method of claim 1, wherein the spherical glass beads in the retroreflective organic solvent-based composition provided in step (b) have a median particle size D50 measured using laser diffraction of between 5 and 100 μm, between 5 and 75 μm, between 5 and 50 μm, between 5 and 45 μm, between 5 and 40 μm, or between 5 and 35 μm.

8. 10. The method of claim 1, wherein at least a portion of the spherical glass beads in the retroreflective organic solvent-based composition provided in step (b) are hemispherically coated with an aluminum coating.

9. 2. The method of claim 1 , wherein the organic solvent in the retroreflective organic solvent-based composition provided in step (b) is selected from the group consisting of aliphatic and aromatic solvents, ketones, esters, glycoethers, alcohols, halogenated hydrocarbons, and combinations thereof.

10. 2. The method of claim 1, wherein the thickening agent in the retroreflective organic solvent-based composition provided in step (b) is selected from the group consisting of (modified) hydrogenated castor oil, clays, modified clays, calcium sulfonate complexes, organophilic phyllosilicates, silica gels, synthetic amorphous silicas, acrylic acid type gelling agents, modified cellulosic materials, polyurea dispersions, solutions of urea modified polyamides, polyurethane dispersions, and combinations thereof.

11. 2. The method of claim 1, wherein the amount of thickener in the retroreflective organic solvent-based composition provided in step (b) is from 0.20 to 3.0 wt %, preferably from 0.25 to 2.5 wt %, more preferably from 0.30 to 2.1 wt %, based on the total weight of the retroreflective organic solvent-based composition provided in step (b).

12. 2. The method of claim 1 , wherein the one or more additional components in the retroreflective organic solvent-based composition provided in step (b) are selected from the group consisting of foam control agents, preservatives, dyes, cure initiators, luminescent agents, pigments, UV absorbers, binders, and resins.

13. 10. The method of claim 1, wherein steps (c), (d) and / or (e) are carried out at a temperature between 15 and 30°C with stirring.

14. 2. The method of claim 1 , wherein step (c) comprises adding the retroreflective organic solvent-based composition provided in step (b) to the non-retroreflective organic solvent-based paste, ink, paint or coating formulation provided in step (a).

15. 2. The method of claim 1, wherein in step (c) the organic solvent based paste, ink, paint or coating formulation without retroreflective properties provided in step (a) is mixed with the retroreflective organic solvent based composition provided in step (b) in a weight ratio of between 40:60 and 60:40, preferably between 45:55 and 55:

45.

16. 2. The method of claim 1, wherein in step (e), the mixture obtained in step (c) or (d) is mixed with 0-2.5 wt%, 0-2.0 wt%, 0-1.8 wt%, 0-1.6 wt%, 0-1.5 wt%, 0-1.4 wt%, or 0-1.3 wt% of a thickener, based on the total weight of the organic solvent based paste, ink, paint, or coating formulation having retroreflective properties obtained in step (c) or (d), respectively.

17. 17. The method of any one of claims 1 to 16, further comprising the step of applying the organic solvent based paste ink, paint or coating formulation having retroreflective properties obtained in step (c), (d) or (e) to a substrate using screen printing, spray coating, curtain coating or spray painting.