Organic solvent-based retroreflective composition for industrial spraying

Abstract

This invention relates to an organic solvent-based reflexive reflective ink, paint, or coating composition having a first Brookfield viscosity η1 between 0.2 and 8 Pa•s at a shear rate of 0.5 rpm and a second Brookfield viscosity η2 between 80 and 450 mPa•s at a shear rate of 20 rpm, provided that η2 is at least twice as low as η1. The organic solvent-based reflexive reflective ink, paint, or coating composition, based on its total weight, comprises: • 25-75 wt% organic solvent; • 1-85 wt% spherical glass beads; • 0.15-1.2 wt% thickener; and • 0-30 wt% one or more other components; wherein the Brookfield viscosities η1 and η2 are measured at 25°C using a #2 spindle in a 600 ml beaker with a diameter of 8.25 cm.

Description

Technical Field

[0001] This invention relates to an organic solvent-based reflexive composition and its preparation method. Further, this invention relates to a method for coating a substrate with a reflexive layer using the organic solvent-based reflexive composition, and the substrate coated with the reflexive layer obtained by this method. Prior Technology

[0002] Reflexive paints, inks, and coatings are used in a variety of applications. For example, they improve the visibility of road signs, road numbering markings, textiles, and automobiles in dark conditions. Paints, inks, and coatings typically provide reflexive properties by adding spherical glass beads with a specific refractive index. Reflexive reflection occurs through a series of refractions: incident light is refracted through the upper surface of the spherical glass bead, internally refracted from the lower surface, and then further refracted as the light leaves the upper surface and travels back in the direction from which the impact light originated.

[0003] WO2004 / 017104A2 discloses a regressive reflective composition comprising regressive reflective microspheres, an adhesive system, and a thixotropic blend comprising at least two thixotropic anti-tack agents in amounts of about 2% to about 5% by weight based on the regressive reflective composition. The regressive reflective composition is intended for use in paints, inks, and coatings and is applied to a substrate using an aerosol applicator with a propellant. Table 1 of WO2004 / 017104A2 discloses typical and preferred amounts of various components in the composition. Example 1 of WO2004 / 017104A2 discloses a composition in which the solvent is an undefined aliphatic or aromatic naphtha, the solid resin particles are of an undefined acrylic type, the first thixotropic adhesive is of an undefined polyurea type, and the second thixotropic adhesive is an undefined calcium sulfonate complex. The accompanying viscosity of the composition in Example 1, measured using a Brookfield #3 spindle at 25°C, was between 9000 and 30000 cps at 0.5 rpm and between 600 and 1900 cps at 20 rpm.

[0004] WO00 / 42113A1 relates to reflexive reflective inks containing microbeads in a liquid carrier medium. The inks are intended for use in screen printing on textiles. WO00 / 42113A1 discloses that the viscosity of screen printing inks, measured at room temperature using a Brookfield viscometer with a #5 spindle rotating at 10 rpm, is between 10 and 30 Pa·s. The inks disclosed in Tables 1-4 and 6 contain water, thickeners, and glass beads. Viscosities measured at room temperature using a Brookfield viscometer with a #5 spindle rotating at 10 rpm are between 12.3 and 32 Pa·s. Screen printing is a printing technique in which a paste-like ink is transferred onto a substrate using a screen, except for areas where the ink does not readily penetrate the stencil. A blade or squeegee moves across the screen to fill the openings in the screen with ink, and then a reverse stroke causes the screen to briefly contact the substrate along the contact lines. This causes the ink to wet the substrate and spring back out of the screen apertures as the screen blades pass through. As is generally known to those familiar with printing techniques, screen printing inks and inks used for professional or industrial (high-speed) spraying have fundamentally different rheological properties because the techniques used to apply them to the substrates are different. Screen printing inks are not suitable for professional or industrial (high-speed) spraying.

[0005] Developing reflexive compositions with good stability, sprayability, and good print or coating quality is very challenging because the rheology modifiers required to maintain the uniform distribution of reflexive particles (such as spherical glass beads with a density generally higher than that of the fluid carrier) in the fluid carrier often adversely affect the rheological properties during spraying.

[0006] The reflex ink, coating, or paint needs to be sufficiently stable and still be easily applied to a variety of substrates using professional or industrial (high-speed) spraying, producing a reflex layer or coating with improved quality.

[0007] Therefore, one object of the present invention is to provide a reflexive composition that can be applied professionally or industrially as paint, ink or coating to a variety of substrates, wherein such reflexive composition can be applied to the substrate by spraying, such as professional or industrial (high-speed) spraying, and wherein such reflexive composition has sufficient stability or shelf life.

[0008] Another objective of this invention is to provide a reflexive reflective composition that can be applied professionally or industrially as paint, ink, or coating to a variety of substrates by spraying, such as professional or industrial (high-speed) spraying, thereby producing improved printing or coating quality, such as good or improved layer uniformity or smoothness. Summary of the Invention

[0009] The inventors unexpectedly determined that one or more of these objectives can be achieved by using one or more organic solvent-based regressive reflective compositions that exhibit shear-dilution behavior and have lower viscosity and reduced thickener concentration at increased shear rates compared to prior art compositions.

[0010] Therefore, in the first embodiment, the present invention provides an organic solvent-based regressive reflective ink, paint, or coating composition having a first Brookfield viscosity η1 at a shear rate of 0.5 rpm between 0.2 and 8 Pa·s, and a second Brookfield viscosity η2 at a shear rate of 20 rpm between 80 and 450 mPa·s, provided that η2 is at least twice as low as η1, wherein, based on the total weight of the composition, the organic solvent-based regressive reflective ink, paint, or coating composition comprises the following: • 25-75% by weight of organic solvent; • 1-85% by weight of spherical glass beads, with a median particle size D50 between 1 and 150 μm as measured by laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; • 0.15 - 1.2% by weight of thickener; and • 0-30% by weight of one or more other ingredients; Brookfield viscosities η1 and η2 were measured at 25°C using a #2 spindle in a 600 ml beaker with a diameter of 8.25 cm.

[0011] The inventors have determined that this organic solvent-based reflexographic composition can be applied to various substrates, for example, using professional or industrial (high-speed) spraying, to produce a reflexographic coating layer with excellent printing or coating quality.

[0012] By reducing the amount of thickener and decreasing viscosity at a shear rate of 20 rpm, a reconflective layer with improved uniformity and smoothness is obtained, specifically a layer with less "orange peel" texture. Reducing the amount of thickener not only decreases viscosity at increased shear rates (representing spraying conditions) but also at low shear rates (related to stability). The inventors have unexpectedly discovered that the reduced amount of thickener required to obtain the reconflective layer with improved uniformity and smoothness remains suitable for providing organic solvent-based reconflective ink, paint, or coating compositions with sufficient stability or shelf life.

[0013] In a second state sample, a method for preparing an organic solvent-based regressive reflective ink, paint, or coating composition as defined herein is provided, the method comprising the following steps: (i) adding to the container an organic solvent, a spherical glass bead as defined above, a thickener as defined above and, as the case may be, one or more of the other ingredients selected as defined above; (ii) preferably stirring or homogenizing the mixture obtained in step (i) at a temperature between 15°C and 70°C, preferably up to a time period between 5 min and 60 min.

[0014] In a third-state sample, the present invention provides a method for coating a substrate with a regressive reflective layer comprising the following steps: a) provide a substrate; b) apply the primer layer to the substrate of step (a) as appropriate; c) as appropriate but not preferably, the coloring base layer is applied to the substrate of step (a) or to the primer layer of step (b); d) spraying an organic solvent-based regressive reflective ink, paint, or coating composition as defined above onto the substrate of step (a) or onto the layer of step (b) or (c); e) drying and / or curing the substrate coated with the reverting reflective layer obtained in step (d); f) Coating with one or more other transparent coating layers as appropriate the warped-dried substrate coated with the reverting reflective layer obtained in step (e).

[0015] In a fourth state sample, the invention relates to a substrate coated with a reverting reflective layer, obtained or available by resorting to a method for coating the substrate as defined herein. definition

[0016] As used herein, the term “orange peel wrinkles” refers to spot-specimen printing defects characterized by a granular image reminiscent of the texture of orange peel wrinkles, caused by the failure of the ink to flow out into the smooth film layer.

[0017] In the context of the organic solvent-based reverting reflective ink, paint, or coating composition of the present invention, the term "shear dilution behavior" relates to a decrease in viscosity when the composition that is initially at rest undergoes a shear rate. Brief explanation of the schema

[0018] Figures 1a to 1h depict the smoothness / orange peel texture of the regressive reflective coatings prepared using the composition according to the present invention and comparative compositions. Implementation

[0019] In the first embodiment, the present invention relates to an organic solvent-based regressive reflective ink, paint, or coating composition having a first Brookfield viscosity η1 at a shear rate of 0.5 rpm between 0.2 and 8 Pa·s, and a second Brookfield viscosity η2 at a shear rate of 20 rpm between 80 and 450 mPa·s, provided that η2 is at least twice as low as η1, wherein, based on the total weight of the composition, the organic solvent-based regressive reflective ink, paint, or coating composition comprises the following: • 25-75% by weight of organic solvent; • 1-85% by weight of spherical glass beads, with a median particle size D50 between 1 and 150 μm as measured by laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; • 0.15 - 1.2% by weight of thickener; and • 0-30% by weight of one or more other ingredients; Brookfield viscosities η1 and η2 were measured at 25°C using a #2 spindle in a 600 ml beaker with a diameter of 8.25 cm.

[0020] In a preferred embodiment, the first sample relates to an organic solvent-based regressive reflective ink, paint, or coating composition having a first Brookfield viscosity η1 at a shear rate of 0.5 rpm between 0.2 and 8 Pa·s and a second Brookfield viscosity η2 at a shear rate of 20 rpm between 80 and 450 mPa·s, provided that η2 is at least twice as low as η1, wherein, based on the total weight of the composition, the organic solvent-based regressive reflective ink, paint, or coating composition comprises the following: • 25-68% by weight of organic solvent; • 20-70% by weight of spherical glass beads, with a median particle size D50 between 5 and 150 μm as measured by laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; • 0.15 - 1.2% by weight of thickener; and • 0-30% by weight of one or more other ingredients; Brookfield viscosities η1 and η2 were measured at 25°C using a #2 spindle in a 600 ml beaker with a diameter of 8.25 cm. [, stability , ]

[0021] In a preferred embodiment, the organic solvent-based regressive reflective ink, paint, or coating composition remains stable for at least 12 hours, more preferably at least 1 day, even more preferably at least 2 days, at least 5 days, at least 10 days, at least 1 month, at least 2 months, at least 6 months, at least 1 year, or at least 2 years, wherein the composition is considered stable if no precipitation or separation can be observed during visual and tactile inspection. In a preferred embodiment, the organic solvent-based regressive reflective ink, paint, or coating composition remains spray-stable for at least 24 hours. The composition is considered spray-stable if it is sprayed without premixing. [, organic solvents , ]

[0022] As used herein, the term "organic solvent" means an organic solvent or a mixture of organic solvents containing less than 3% by weight of water, preferably less than 2% by weight of water, more preferably less than 1% by weight of water, even more preferably less than 0.5% by weight of water, and most preferably free of water.

[0023] Preferred organic solvents are selected from the group consisting of: aliphatic and aromatic solvents, ketones, esters, glycol ethers, alcohols, halogenated hydrocarbons and combinations thereof. Excellent organic solvents are selected from the group consisting of: xylene (a mixture of isomers), toluene, ethylbenzene, naphtha, 1,2,4-trimethylbenzene, trimethylbenzene, n-propylbenzene, isoamyl acetate, n-butyl acetate, (2-methoxymethylethoxy)propanol, 2-butoxyethyl acetate, 2-methylbutyl acetate, isobutanol, 1-butanol, 1-ethoxypropane-2-ol, 2,6-dimethyl-4-heptanone, 2-methoxy-1-methylethyl acetate, 4,6-dimethyl-heptane-2-one, 4-methyl-2-pentanone, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, 2-(2-butoxyethoxy)ethanol, 2-butoxyethanol, 5-methylhexane-2-one, ethyl acetate, and combinations thereof.

[0024] In a preferred embodiment, the amount of organic solvent is 25-68% by weight, based on the total weight of the organic solvent-based reconductive ink, coating, or paint composition.

[0025] In a preferred embodiment, the amount of organic solvent is 27-65% by weight, more preferably 30-60% by weight, or even more preferably 35-58% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0026] In the embodiments, the amount of organic solvent is 25-66% by weight, 25-62% by weight, 25-60% by weight, 25-58% by weight, or 25-56% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0027] In other embodiments, the amount of organic solvent is 28-68% by weight, 30-68% by weight, 32-68% by weight, 34-68% by weight, 36-68% by weight, 38-68% by weight, or 40-68% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0028] In other embodiments, the amount of organic solvent is 28-75% by weight, 30-75% by weight, 32-75% by weight, 34-75% by weight, 36-75% by weight, 38-75% by weight, or 40-75% by weight, based on the total weight of the organic solvent-based reconvertible ink, coating, or paint composition. [, Spherical glass beads , ]

[0029] As defined above, the refractive index of a spherical glass bead measured at a wavelength λ of 589 nm is between 1.5 and 2.8.

[0030] In a preferred embodiment, the refractive index of the spherical glass bead, measured at a wavelength λ of 589 nm, is: (a) Between 2.0 and 2.8, preferably between 2.1 and 2.4; or (b) Between 1.7 and 2.1, preferably between 1.8 and 2.0.

[0031] In a preferred embodiment, as used herein, the term "glass" in "spherical glass bead" refers to a non-crystalline, amorphous solid and transparent material made of oxides. In other embodiments, the term "glass" in "spherical glass bead" refers to a solid and transparent material made of oxides and containing some microcrystalline properties. The refractive index of a spherical glass bead is closely related to the density of the glass, although the relationship is not linear. Due to the properties of glass, density is approximately an additive function of its components. The density of spherical glass beads with a refractive index between 1.5 and 2.8 typically varies between 2.5 and 4.5 g / cm³.

[0032] The oxides that can be used in 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, for example, different combinations of the following: silicon dioxide (SiO₂), boron oxide (B₂O₃), phosphorus pentoxide (P₂O₅), vanadium pentoxide (V₂O₅), arsenic trioxide (As₂O₃), germanium oxide (GeO₂), calcium oxide (CaO), sodium oxide (Na₂O), magnesium oxide (MgO), zinc oxide (ZnO), aluminum oxide (Al₂O₃), potassium oxide (K₂O), ferric oxide (Fe₂O₃), lead oxide (PbO), barium oxide (BaO), barium titanate (BaTiO₃), titanium dioxide (TiO₂), lithium oxide (Li₂O), strontium oxide (SrO), lanthanum oxide (La₂O₃), and zirconium dioxide (ZrO₂). Silicon dioxide and boron oxide typically have the lowest densities. Glasses containing a large percentage of these oxides generally produce glass beads with low refractive indices. The refractive index is increased by adding oxides with higher molecular weight. Preferably, the spherical glass beads do not contain PbO.

[0033] Glass beads with a refractive index ranging from 1.5 to 2.51 and composed of oxides are disclosed in WO2014 / 109564A1, which is incorporated herein by reference in its entirety. Transparent glass beads without PbO and with a refractive index greater than 2.15 are disclosed in US4,082,427, which is incorporated herein by reference in its entirety.

[0034] Spherical glass beads can be colored spherical glass beads, as long as they remain transparent. This invention covers colored spherical glass beads made of colored transparent glass and spherical glass beads provided with concentric transparent colored coatings. The color can be a natural color caused by the composition of oxides or can be selected by deliberately adding colorimetric components. Colored glass beads with high refractive index and high transparency are disclosed in WO2014 / 109564A1.

[0035] Therefore, in one embodiment, at least a portion of the spherical glass beads are glass beads made of colored transparent glass and / or at least a portion of the spherical glass beads are provided with a concentric transparent colored coating.

[0036] Spherical glass beads have a median particle size D50, as measured using laser diffraction. Therefore, based on volume distribution, the median particle size D50 is the volume median value. The median particle size D50 is the diameter below which a group of half of the spherical glass beads is smaller. This volume median particle size is commonly referred to in this technique as Dv50 or Dv0.5.

[0037] In a preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 5 and 150 μm.

[0038] In one embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 25 and 100 μm, preferably between 30 and 75 μm, and more preferably between 35 and 50 μm.

[0039] In a preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 5 and 100 μm, such as 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.

[0040] In a preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 1 and 100 μm, such as 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.

[0041] In yet another embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 25 and 150 μm, such as between 50 and 150 μm, 75 and 150 μm, 100 and 150 μm, 110 and 150 μm, or 115 and 150 μm.

[0042] In this technology, diameters D10 and D90 are typically referred to as Dv10 or Dv0.1 and Dv90 or Dv0.9, respectively. The D10 diameter is the diameter below which 10% of the spherical glass beads are smaller. Similarly, the D90 diameter is the diameter below which 90% of the spherical glass beads are smaller.

[0043] The particle size distribution of spherical glass beads, as measured by laser diffraction, is defined by the following:

[0044] In another embodiment, the spherical glass beads, when measured by laser diffraction, have a median particle size D50 between 15 and 100 μm and a span between 0 and 1.9, such as between 0 and 1.5, 0 and 1, 0 and 0.5, 0 and 0.2, or 0 and 0.1.

[0045] In yet another embodiment, the spherical glass beads, when measured by laser diffraction, have a median particle size D50 between 30 and 75 μm and a span between 0 and 1.9, such as between 0 and 1.5, 0 and 1, 0 and 0.5, 0 and 0.2, or 0 and 0.1.

[0046] In another preferred embodiment, the spherical glass beads, when measured by laser diffraction, have a median particle size D50 between 15 and 50 μm and a span between 0 and 1.9, such as between 0 and 1.5, 0 and 1, 0 and 0.5, 0 and 0.2, or 0 and 0.1.

[0047] In yet another preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 1 and 35 μm, and the span is 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.

[0048] In yet another preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 5 and 35 μm, and the span is 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 preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 10 and 25 μm, and the span is 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 yet another preferred embodiment, the spherical glass beads, when measured by laser diffraction, have a median particle size D50 of 1 to 25 μm and a span between 0 and 1.9, such as between 0 and 1.5, 0 and 1, 0 and 0.5, 0 and 0.2, or 0 and 0.1.

[0051] In yet another preferred embodiment, the spherical glass beads, when measured by laser diffraction, have a median particle size D50 of 1 to 15 μm and a span between 0 and 1.9, such as between 0 and 1.5, 0 and 1, 0 and 0.5, 0 and 0.2, or 0 and 0.1.

[0052] In yet another preferred embodiment, the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 1 and 10 μm, and the span is 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] As those familiar with this technique understand, a span of 0 corresponds to a monodisperse spherical glass bead.

[0054] In a preferred embodiment, at least a portion of the spherical glass beads are coated with a light-reflective coating, preferably a hemispherical aluminum coating (HAC). In another embodiment, at least a portion of the spherical glass beads are coated with a fluorine chemical coating.

[0055] In a preferred embodiment, the amount of spherical glass beads is 20-70% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0056] In a preferred embodiment, the amount of spherical glass beads is 23-68% by weight, more preferably 25-65% by weight, and even more preferably 28-63% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating or paint composition.

[0057] In the embodiments, the amount of spherical glass beads is 20-65% by weight, 20-63% by weight, 20-60% by weight, 20-57% by weight, 20-54% by weight, 20-52% by weight, or 20-50% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0058] In the embodiments, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition, the amount of spherical glass beads is 1-80% by weight, 1-78% by weight, 1-76% by weight, 1-74% by weight, 1-72% by weight, 1-70% by weight, or 1-68% by weight.

[0059] In other embodiments, the amount of spherical glass beads is 22-70% by weight, 24-70% by weight, 26-70% by weight, 27-70% by weight, 28-70% by weight, 29-70% by weight, or 30-70% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0060] In other embodiments, the amount of spherical glass beads is 2-85% by weight, 5-85% by weight, 8-85% by weight, 10-85% by weight, 12-85% by weight, 14-85% by weight, or 16-85% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0061] The specific application of an organic solvent-based relativistic ink, coating, or paint composition determines the optimal refractive index of the spherical glass beads. If the composition is intended for use in a dry environment or on a substrate displaying relativistic reflection under dry conditions, and the applied layer of the relativistic spherical glass beads is not coated with another layer, the refractive index of the spherical glass beads, measured at a wavelength λ of 589 nm, can be between 1.8 and 2.8.

[0062] In one embodiment, an organic solvent-based reflexive ink, coating, or paint composition as defined herein comprises spherical glass beads with a refractive index between 1.8 and 2.0 as measured at a wavelength λ of 589 nm.

[0063] On the other hand, if the composition is intended for use in a humid environment or on a substrate exhibiting relativistic reflection under humid conditions, or if the applied layer of the relativistic spherical glass beads is coated with one or more other transparent layers, then the refractive index of the spherical glass beads, measured at a wavelength of 589 nm λ, is preferably between 2.0 and 2.8, more preferably between 2.2 and 2.4. Compositions exhibiting relativistic reflection under both dry and humid conditions, wherein the applied layer of the relativistic spherical glass beads is coated with one or more other transparent layers or uncoated, may comprise different types of glass beads with different refractive indices and, where appropriate, different sizes. In one embodiment, an organic solvent-based relativistic ink, coating, or paint composition, as defined herein, comprises spherical glass beads with a refractive index measured at a wavelength of 589 nm λ between 2.0 and 2.8, preferably between 2.2 and 2.4.

[0064] In another embodiment, the organic solvent-based reflexive ink, coating, or paint composition as defined herein comprises at least two types of spherical glass beads, wherein at least one type of spherical glass beads has a refractive index between 1.8 and less than 2.0 as measured at a wavelength of 589 nm, and at least one other type of spherical glass beads has a refractive index between 2.0 and 2.8 as measured at a wavelength of 589 nm. [, Thickener , ]

[0065] Organic solvent-based reflexive reflective ink, coating, or paint compositions contain thickeners. It is not intended to be bound by any theory, but it is believed that thickeners limit or reduce the settling and / or precipitation of spherical glass beads and, where appropriate, other particulate matter in organic solvent-based reflexive reflective ink, coating, or paint compositions, allowing the composition to be easily resuspended. Furthermore, it is not intended to be bound by any theory, but it is believed that thickeners provide organic solvent-based reflexive reflective ink, coating, or paint compositions with shear-dilution behavior.

[0066] In a preferred embodiment, the thickener comprises a mixture of different thickeners.

[0067] Preferred examples of thickeners suitable for use in organic solvent-based recontrast inks, coatings, or paint compositions are selected from the group consisting of: (modified) halogenated castor oil, clay, modified clay, calcium sulfonate complexes, organophilic layered silicates, silicone, synthetic amorphous silica, acrylic gelling agents, modified cellulose materials, polyurea dispersions, urea-modified polyamide solutions, polyurethane dispersions, and combinations thereof.

[0068] Examples of modified clays include BENTONE® LT and BENTONE® 38 (Elementis Global). Examples of silicones include HDK® N20 (Wacker Chemical Corporation) and AEROSIL® (Evonik). Examples of organophilic layered silicates include Claytone 40 (Byk). Examples of modified halogenated castor oil include Efka® RM 1900 (BASF). Examples of halogenated castor oil include Efka® RM 1920 (BASF). A solution of urea-modified nonpolar polyamide in isobutanol / monophenyl glycol is Rheobyk-431 (Byk). A solution of moderately polar urea-modified polyamide in isobutanol / solvent naphtha is Rheobyk-430 (Byk). An example of synthesizing amorphous silica is Zeothix® (Huber).

[0069] In a preferred embodiment, two thickeners are used in the organic solvent-based regressive reflective ink, coating, or paint composition, more preferably: • Organic-friendly layered silicates and modified halogenated castor oil; or • Calcium sulfonate complexes and polyurea dispersions.

[0070] In a preferred embodiment, the amount of thickener is 0.20-1.18 wt%, more preferably 0.25-1.15 wt%, and even more preferably 0.30-1.10 wt%, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0071] In the embodiments, the amount of thickener is 0.15-1.18% by weight, 0.15-1.15% by weight, or 0.15-1.10% by weight, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0072] In other embodiments, the amount of thickener is 0.20-1.20 wt%, 0.30-1.20 wt%, 0.40-1.20 wt%, 0.45-1.20 wt%, or 0.50-1.20 wt%, based on the total weight of the organic solvent-based regressive reflective ink, coating, or paint composition.

[0073] The amount of organic solvent in an organic solvent-based recontrast ink, coating, or paint composition is specified independently. If the thickener is applied, for example, as a dispersion in a solvent, the amount of thickener as defined above refers to the dry weight of the thickener. [, Other ingredients , ]

[0074] As described above, compositions of organic solvent-based reflexive inks, paints, or coatings contain 0-30% by weight of one or more other ingredients. As those skilled in the art will understand, "other" ingredients are different from the other ingredients defined in compositions of organic solvent-based reflexive inks, paints, or coatings. In other words, other ingredients do not include spherical glass beads, thickeners, and organic solvents.

[0075] In a preferred embodiment, one or more other components are selected from the group consisting of: foam control agents, luminescent agents, UV absorbers, adhesives and resins, preservatives, dyes, pigments and curing initiators.

[0076] Suitable binders and resins used in organic solvent-based compositions are generally known to those skilled in the art. The binder or resin may be radiation-cured. If the binder or resin is radiation-cured, other components may include a curing initiator, such as a photoinitiator or a thermal initiator.

[0077] In one embodiment, the organic solvent-based regressive reflective ink, paint, or coating composition comprises, as part of one or more other components, a synthetic pigment flake having an average diameter between 5 and 50 μm, a thickness of less than 1 μm, and an aspect ratio (flake diameter / thickness) of at least 10, wherein the synthetic pigment flake is selected from (A), (B), (C), or a combination thereof: (A) A metal sheet or synthetic mica sheet, which, as appropriate, is coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, low-valent titanium oxides, titanium oxynitride, FeO(OH), SiO2, B2O3, GeO2, MgF2, metal alloys, and rare earth compounds, and, as appropriate, is coated with an outer layer containing one or more colorants and adhesives; (B) A sheet comprising Al₂O₃, SiO₂, glass, ceramic, graphite, and mica flakes, wherein, as appropriate, it is coated with at least one layer of one or more components selected from the group consisting of metal oxides, metals, metal sulfides, low-valent titanium oxides, titanium oxynitride, FeO(OH), SiO₂, B₂O₃, GeO₂, metal alloys, and rare earth compounds, and wherein, as appropriate, it is coated with an outer layer comprising one or more colorants and adhesives; (C) A sheet containing Al₂O₃ flakes doped with one or more components selected from the group consisting of TiO₂, ZrO₂, SiO₂, SnO₂, In₂O₃, ZnO, and iron oxide, and which, depending on the case, is coated with at least one layer selected from the group consisting of metal oxides, metals, metal sulfides, low-valent titanium oxides, titanium oxynitride, FeO(OH), SiO₂, B₂O₃, GeO₂, metal alloys, and rare earth compounds, and which, depending on the case, is coated with an outer layer containing one or more colorants and binders; In the context of synthetic pigment flakes, the term "average diameter" refers to the median particle size D50.

[0078] As those familiar with this technique will understand, the term "synthetic" in "synthetic pigment flakes" means that the pigment flakes are not naturally occurring pigment flakes, but rather that they are chemically manufactured pigment flakes or naturally occurring pigment flakes that have undergone chemical / physical treatment. One advantage of using synthetic pigment flakes is that they can produce very smooth surfaces, thereby increasing their reflective properties.

[0079] As used herein, the terms "flake" or "particle" refer to a pigment shape having a large surface area and a small thickness. Typically, a flake or particle is characterized by its "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). As used herein, the aspect ratio of synthetic pigment flakes is at least 10, preferably at least 15, and more preferably at least 20.

[0080] In a preferred embodiment, the average diameter of the composite sheet is 6-45 μm, more preferably 7-35 μm, even more preferably 8-25 μm, still more preferably 9-20 μm, and most preferably 10-16 μm.

[0081] In a preferred embodiment, the thickness of the composite sheet is between 10 nm and 800 nm, more preferably between 15 nm and 600 nm. In another preferred embodiment, the thickness of the composite sheet is between 10 and 200 nm, more preferably between 10 and 150 nm, even more preferably between 10 and 100 nm, and still more preferably between 10 and 50 nm.

[0082] In the embodiments, based on the total weight of the organic solvent-based regressive reflective ink, paint or coating composition, the amount of one or more other components is 0-25% by weight, 0-20% by weight, 0-15% by weight, 0-12% by weight, 0-10% by weight, 0-8% by weight, 0-6% by weight or 0-5% by weight.

[0083] In other embodiments, based on the total weight of the organic solvent-based regressive reflective ink, paint, or coating composition, the amount of one or more other components is 0.1-23% by weight, 0.5-17% by weight, or 1-15% by weight.

[0084] The amount of organic solvent in an organic solvent-based regressive reflective ink, paint, or coating composition is specified independently. If one or more other components are applied in the form of, for example, a solution, suspension, or dispersion in a solvent, the amount of one or more other components as defined above refers to the dry weight of one or more other components, i.e., the weight excluding solvent. [, rheological behavior , ]

[0085] Organic solvent-based regressive reflective inks, paints, or coatings exhibit shear-dilution behavior. This means that the composition has a viscosity that decreases when its static / steady state is disturbed by subjecting it to a certain increased shear rate.

[0086] As defined above, the first Brookfield viscosity η1 of an organic solvent-based regressive reflective ink, paint, or coating composition, as defined herein, is between 0.2 and 8 Pa·s at a shear rate of 0.5 rpm, and the second Brookfield viscosity η2 is between 80 and 450 mPa·s at a shear rate of 20 rpm, provided that η2 is at least twice as low as η1, as measured using a #2 spindle in a 600 ml beaker with a diameter of 8.25 cm at 25°C.

[0087] In one preferred embodiment, η1 is between 0.25 and 5 Pa·s and η2 is between 100 and 425 mPa·s, provided that η2 is at least twice as low as η1. In another preferred embodiment, η1 is between 0.26 and 2.5 Pa·s and η2 is between 110 and 400 mPa·s, provided that η2 is at least twice as low as η1. In yet another preferred embodiment, η1 is between 0.27 and 2 Pa·s and η2 is between 120 and 350 mPa·s, provided that η2 is at least twice as low as η1.

[0088] The first viscosity η1 of the organic solvent-based regressive reflective ink, paint, or coating composition, determined at a shear rate of 0.5 rpm, is sufficient to retain spherical glass beads and other particulate materials, selected as appropriate, in suspension for a sufficiently long period. For (industrial) spraying conditions, a shear rate of 20 rpm is typical, under which the organic solvent-based regressive reflective ink, paint, or coating composition can be applied to the substrate. The second viscosity η2 is sufficiently low to provide an easily sprayable organic solvent-based regressive reflective ink, paint, or coating composition.

[0089] In a preferred embodiment, the third Brookfield viscosity η3 of the organic solvent-based regressive reflective ink, paint, or coating composition as defined herein is less than 1.5 Pa·s, more preferably less than 1.3 Pa·s, and even more preferably less than 1.1 Pa·s, such as less than 1.0 Pa·s, less than 0.8 Pa·s, or less than 0.6 Pa·s, as measured using a #5 spindle in a 600 ml beaker with a diameter of 8.25 cm at 25°C.

[0090] In another preferred embodiment, the fourth Brookfield viscosity η4 of the organic solvent-based regressive reflective ink, paint, or coating composition, as defined herein, is between 0.25 and 5 Pa·s at a shear rate of 0.5 rpm, and the fifth Brookfield viscosity η5 is between 80 and 450 mPa·s at a shear rate of 20 rpm, provided that η5 is at least twice as low as η4, as measured using a #3 spindle in a 600 ml beaker with a diameter of 8.25 cm at 25°C.

[0091] In yet another preferred embodiment, the fourth Brookfield viscosity η4 of the organic solvent-based regressive reflective ink, paint, or coating composition, as defined herein, is between 0.30 and 3 Pa·s at a shear rate of 0.5 rpm, and the fifth Brookfield viscosity η5 is between 100 and 425 mPa·s at a shear rate of 20 rpm, provided that η5 is at least twice as low as η4, as measured using a #3 spindle in a 600 ml beaker with a diameter of 8.25 cm at 25°C.

[0092] In yet another preferred embodiment, the organic solvent-based regressive reflective ink, paint, or coating composition, as defined herein, has a fourth Brookfield viscosity η4 between 0.35 and 2.5 Pa·s at a shear rate of 0.5 rpm and a fifth Brookfield viscosity η5 between 110 and 400 mPa·s at a shear rate of 20 rpm, provided that η5 is at least twice as low as η4, as measured using a #3 spindle in a 600 ml beaker with a diameter of 8.25 cm at 25°C. [, Method for preparing composition of organic solvent-based reflexive inks, paints, or coatings , ]

[0093] Generally, the components of an organic solvent-based reconvertible ink, coating, or paint composition can be added in any order. However, it is preferable to add the thickener at the end of the process, at least after the spherical glass beads are added to the organic solvent, because it is more difficult to evenly distribute these components in the thickened composition.

[0094] In one preferred embodiment, the thickener is added after the organic solvent is mixed with the spherical glass beads. In another preferred embodiment, the thickener is added after the organic solvent, spherical glass beads, and any other components are mixed. Stirring or homogenization is preferably performed at a low shear rate to avoid the inclusion of air bubbles in the organic solvent-based reconvertible reflective ink, coating, or paint composition.

[0095] In the second state, a method for preparing an organic solvent-based reflexive reflective ink, coating, or paint composition as defined herein is provided, the method comprising the following steps: (i) Add the organic solvent, spherical glass beads as defined above, thickener as defined above, and, as appropriate, one or more other ingredients as defined above to the container; and (ii) The mixture obtained in step (i) is stirred or homogenized at a temperature between 15°C and 70°C for a period of time between 5 minutes and 60 minutes.

[0096] However, the addition of different components is also carried out at different stages of this method. Therefore, in one embodiment, a method is provided for preparing an organic solvent-based reflexive reflective ink, coating, or paint composition as defined herein, the method comprising the following steps: (i) Add an organic solvent, spherical glass beads as defined above, at least a portion of a thickener as defined above, and, as appropriate, a portion of one or more other ingredients as defined above to the container; (ii) The mixture obtained in step (i) is preferably stirred or homogenized at a temperature between 15°C and 70°C for a period of 5 to 60 minutes; (iii) Add at least a portion of one or more other ingredients as defined above to the composition obtained in step (ii) or (iii), and, where appropriate, add a portion of a thickener as defined above and, where appropriate, an organic solvent; and (iv) The mixture obtained in step (iii) is stirred or homogenized at a temperature between 15°C and 70°C for a period of time between 5 minutes and 60 minutes.

[0097] In the embodiments, the time between steps (i) and (ii) and between steps (iii) and (iv) can be several days, months or longer.

[0098] A method for preparing an organic solvent-based reflexive ink, coating, or paint composition may also include producing an intermediate organic solvent-based reflexive ink, coating, or paint composition having the composition and properties described above, followed by adding and mixing another composition to obtain a final organic solvent-based reflexive ink, coating, or paint composition, provided that the final organic solvent-based reflexive ink, coating, or paint composition still has the composition and properties described above.

[0099] Therefore, in one embodiment, a method is provided for preparing an organic solvent-based reflexive reflective ink, coating, or paint composition as defined herein, the method comprising the following steps: (i) Add an organic solvent, spherical glass beads as defined above, at least a portion of a thickener as defined above, and, as appropriate, a portion of one or more other ingredients as defined above to the container; (ii) Preferably, the mixture obtained in step (i) is stirred or homogenized at a temperature between 15°C and 70°C for a period of time between 5 and 60 minutes to obtain an intermediate organic solvent-based reflexive ink, coating or paint composition having the composition and properties of an organic solvent-based reflexive ink, coating or paint composition as defined above; (iii) Add at least a portion of one or more other components as defined above to the intermediate organic solvent-based reversion reflective ink, coating, or paint composition obtained in step (ii), and, where appropriate, add a portion of a thickener as defined above and, where appropriate, an organic solvent; and (iv) Preferably, the mixture obtained in step (iii) is stirred or homogenized at a temperature between 15°C and 70°C for a period of time between 5 minutes and 60 minutes to obtain an organic solvent-based reversion reflective ink, coating or paint composition.

[0100] In the embodiments, the time between steps (i) and (ii) and between steps (iii) and (iv) can be several days, months or longer. [, Method for coating substrates , ]

[0101] In the third state, the present invention relates to a method for coating a substrate with a restoring reflective layer, the method comprising the following steps: a) Provide a substrate; b) Apply a primer layer to the substrate from step (a) as needed; c) Depending on the circumstances, but not necessarily better, apply the colored base layer to the substrate of step (a) or the primer layer of step (b); d) Spray the organic solvent-based reversion reflective ink, coating, or paint composition as defined above onto the substrate of step (a) or the layer of step (b) or (c); e) Drying and / or curing the substrate coated with the restorative reflective layer obtained in step (d); and f) Apply one or more additional transparent coating layers to the dried substrate coated with the restorative reflective layer obtained in step (e), and then dry and / or cure.

[0102] Step (d) of spraying an organic solvent-based recontrast ink, coating, or paint composition can consist of spraying a single layer in one step or spraying multiple layers on top of each other in subsequent spraying steps. Subsequent layers are preferably applied "wet-in-wet," meaning that the later layer is applied over the previous one, at least some to virtually all of the organic solvent evaporates from that layer, but is not (fully) cured. This means that even when subsequent layers are applied "wet-in-wet," an intermediate drying step is applied between the application of subsequent layers.

[0103] Drying between layers is typically carried out at a temperature between 20°C and 30°C for about 2 to 15 minutes.

[0104] It is also possible to completely dry and / or cure the previous layer before applying the next layer. Complete drying and / or curing of a layer typically takes about 20 or 30 minutes at a temperature of about 60°C, or about 20°C in open air. Choosing appropriate drying conditions is within the skill of a technician.

[0105] In one embodiment, step (d) includes spraying more than one layer, such as 2, 3, 4 or 5 layers.

[0106] In one embodiment, step (d) includes n subsequent spraying steps to produce n layers, wherein layer x is at least partially applied to layer x-1, where x is an integer between 2 and n, and where n is an integer between 2 and 5.

[0107] In a preferred embodiment, the organic solvent-based reconvertible ink, coating, or paint composition is applied in step (d) at an amount of 100-800 g / m² substrate, more preferably 100-400 g / m² substrate.

[0108] In one embodiment, step (b) is omitted. In a preferred embodiment, step (c) is omitted.

[0109] The geometry of the substrate to be coated is not limited in any sense, as long as it can be coated by spraying, that is, as long as droplets of the organic solvent-based regressive ink, coating, or paint composition can reach the surface of the substrate. In one embodiment, the substrate is planar. In other embodiments, the substrate is curved. In other embodiments, the substrate includes both planar and curved portions.

[0110] The inventors have determined that organic solvent-based reflexive ink, coating, or paint compositions can be applied to various substrates, for example, using professional or industrial (high-speed) spraying, to produce reflexive coating layers with excellent printing or coating qualities, such as uniformity and reflexive reflection at wide angles. These results can be obtained when organic solvent-based reflexive ink, coating, or paint compositions are applied to the surface of a vertically positioned substrate, even when sprayed from below.

[0111] If the reflexive coating layer is provided with one or more other transparent coating layers (i.e., performing step (f) of the method for coating a substrate as defined herein), a reflexive coating layer with high smoothness and improved cleanability is obtained.

[0112] In a preferred embodiment, the substrate is selected from textiles, leather, metals, concrete, rubber, plastics, carbon fiber, and combinations thereof. As used herein, textiles include woven or knitted fabrics such as cotton, polyester, nylon, silk, wood, rubber fibers, and acrylic.

[0113] Regardless of the type of material the substrate is made of, the substrate can be selected from the following groups: clothing, traffic signs, car chassis or body, bicycle frame, road, road surface and guardrail.

[0114] A substrate having the reflexive coating according to the invention may be provided with one or more other transparent coating layers in step (f). These one or more other transparent coating layers may be used to protect the reflexive layer from damage and / or moisture. Furthermore, they may be used to provide a substrate coated with a reflexive layer having a specific matte and / or glossy / smooth appearance. The one or more other transparent coating layers may be colored. The one or more other transparent coating layers applied in step (f), as selected as appropriate, may comprise a liquid coating layer, a powder coating layer, or a combination thereof that is subsequently cured or dried.

[0115] If one or more other transparent coating layers are to be applied in step (f) to the organic solvent-based recontrast ink, coating, or paint composition layer, the organic solvent-based recontrast ink, coating, or paint composition layer is typically not fully cured. Selecting appropriate drying conditions is within the skill of a person skilled in the art.

[0116] The spraying in step (c) is preferably performed using a curtain coating, spray gun, high-speed rotating cup, or a spray can containing propellant. In a preferred embodiment, the spraying is performed without the use of propellant.

[0117] In the fourth embodiment, the present invention relates to a substrate coated with a reflexive reflective layer, which is obtained or can be obtained by the method defined above. The substrate coated with the reflexive reflective layer can have a matte or glossy appearance.

[0118] In a preferred embodiment, a substrate coated with a reflexive reflective layer, preferably coated with one or more other transparent coating layers (i.e., performing step (e) of the method for coating the substrate as described above), displays reflexive reflection perpendicular to the coated substrate at any angle between 0 and 80°, such as between 0 and 78°, 0 and 75°, 0 and 70°, 0 and 65°, 0 and 60°, 0 and 55°, 0 and 50°, 0 and 45°, and 0 and 40°. Reflexive reflection of the reflexive reflective layer is determined by guiding a torch beam to the reflexive reflective layer (where the line of sight of the eye substantially coincides with the torch beam) and by visually determining whether reflexive reflection is observed. The experiment begins at zero angle relative to the coated substrate, and this angle is gradually increased until reflexive reflection is indistinguishable.

[0119] Therefore, the present invention has been described with reference to certain embodiments discussed above. It should be recognized that these embodiments are readily adaptable to various modifications and alternative forms are well known to those skilled in the art.

[0120] Furthermore, for proper understanding of this document and its requests, the verb "to comprise" and its variations should be understood to be used without limitation, meaning to include the items following the word, but not excluding items specifically mentioned. Additionally, unless the context explicitly requires the presence of one and only one element, the indefinite article "a / an" referring to one element does not preclude the possibility of more than one element. Therefore, the indefinite article "a / an" generally means "at least one". [Example] Viscosity measurement scheme

[0121] Viscosities were measured at 25°C using a Brookfield Ametek® DV2T viscometer with different standardized spindles (#2, #3, and #5; LV-2, LV-3, and LV-5 from Brookfield Ametek®) according to the operating instructions. Measurements were performed in 600 ml low-form Griffin beakers with flat bottoms and a diameter of 8.25 cm without the use of guards. Before measuring viscosity, the samples were heated to 25°C and homogenized using stirring. Example 1

[0122] Four compositions (samples 2, 4, 5, and 7) and four comparative compositions (samples 1, 3, 6, and 8) according to the present invention were prepared in kg units. The following ingredients were used: Spherical glass beads: • Microscopic glass beads (RI 2.2), obtained from Jiangxi Sunflex Light Retroreflective Material Co., Ltd., have a refractive index of approximately 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, measured using laser diffraction, and a specific gravity of approximately 4.5 g / cm³. These spherical glass beads contain TiO₂, BaO, CaO, SiO₂, and ZnO. • Microscopic glass beads (RI 1.9, HAC), obtained from Jiangxi Sunflex Light Retroreflective Material Co., Ltd., are hemispherical aluminum-coated glass beads with a refractive index of approximately 1.9 measured at a wavelength λ of 589 nm. The median particle size D50 is 38.22 μm, the D10 diameter is 34.86 μm, and the D90 diameter is 43.04 μm, measured using laser diffraction. The specific gravity is approximately 4.2 g / cm³. These spherical glass beads contain TiO₂, BaO, SiO₂, CaO, and Al₂O₃. organic solvents The solvent portion of Cromax XB165 Centari 6000 Low Emission Binder (Axalta) is a mixture of organic solvents, including xylene, toluene, ethylbenzene, isoamyl acetate, n-butyl acetate, isobutanol, and 2-methoxy-1-methylethyl acetate. Cromax XB383 (Axalta) contains a mixture of organic solvents such as xylene, ethylbenzene, naphtha, 1,2,4-trimethylbenzene, n-propylbenzene, isoamyl acetate, n-butyl acetate, 2-methylbutyl acetate, and 4-methyl-2-pentanone. Cromax AU370 / Imron® 700 polyurethane thinner (Axalta) contains xylene, ethyl acetate, n-butyl acetate, ethylbenzene, isopentyl acetate, 2-methylbutyl acetate, and toluene. • Avatar T-4500 (obtained from the Global Refinish Trading Center, Cyprus), an acrylic thinner containing dimethylbenzene (a mixture of isomers), n-butyl acetate, 1-methoxy-2-propyl acetate, ethylbenzene, and 2-(2-butoxyethoxy)ethanol. The solvent portion of Aquamet® CP-BG / 8500 / 60 is obtained from Schlenk Metallic Pigments GmbH, and contains butanediol. Other ingredients • Adhesive component of Cromax XB165 Centari 6000 Low Emission Binder • Aquamet® CP-BG / 8500 / 60 solid fraction, obtained from Schlenk Metallic Pigments GmbH, consists of silicon dioxide-coated aluminum flakes with an average diameter of approximately 16 μm and a thickness of < 1 μm. Xirallic® T61-10 WNT Micro Silver, obtained from Merck KGaA, is a coated alumina sheet with an average diameter between 8 and 14 μm and a thickness of < 1 μm. Thickener • Efka® RM 1900, obtained from BASF, modified halogenated castor oil, fine powder thickener • Efka®RM 1920, from BASF, halogenated castor oil, fine powder, thickener • Claytone 40, obtained from Byk, is an organophilic layered silicate and a thickener. Four compositions (samples 2, 4, 5 and 7) and four comparative compositions (samples 1, 3, 6 and 8) according to the present invention were prepared by adding the ingredients in the following order to a container (3.5 liters): (1) Add an organic solvent, such as Avatar T-4500, at ambient temperature (-20℃) and start stirring at 500 rpm; (2) Add glass beads at ambient temperature (-20℃) and mix at 500 rpm for at least 5 minutes; (3) Add a thickener, such as Claytone 40, at ambient temperature (-20°C) and mix at 1300 rpm for at least 5 minutes, slowly increasing the rpm to 2000 rpm without introducing air bubbles; (4) Add a thickener, such as Efka® RM 1900 and / or Efka® RM 1920, and continue stirring at 1800 rpm for at least 45 minutes, increasing the rpm further if necessary, without introducing air bubbles; (5) Add other ingredients, such as Cromax XB165 and pigment flakes, and mix at 2000 rpm. Continue mixing at 2000 rpm for at least 15 minutes. (6) Add additional thickener as needed, then stir for another 15 minutes at about 1800 rpm. The amounts of the different components are listed in Table 1. Table 1 [sample] [Comparison 1] [2] [Comparison 3] [4] [5] [Comparison 6] [7] [Comparison 8] Element [weight%] [weight%] [weight%] [weight%] [weight%] [weight%] [weight%] [weight%] [Organic solvents] [, ⑴ , ] Cromax XB165 33.39 33.77 30.11 29.48 35.38 35.05 35.35 35.04 Cromax XB383 17.03 17.25 25.61 25.81 Cromax AU370 17.26 17.06 Avatar T-4500 18.00 17.84 Aquamet CP-BG / 8500 / 60 1.64 1.64 [Subtotal Organic Solvents] (1) [52.06] [52.67] [55.72] [55.30] [52.64] [52.11] [53.35] [52.88] [Spherical glass beads] 2.2 glass beads 31.32 32.13 36.43 36.12 1.9 HAC glass beads 34.41 34.85 36.87 36.44 [Subtotal of spherical glass beads] [34.41] [34.85] [31.32] [32.13] [36.87] [36.44] [36.43] [36.12] Other ingredients, (2) , ] Aquamet CP-BG / 8500 / 60 2.46 2.47 Xirallic T61-10 WNT Micro Silver 3.64 3.57 Cromax XB155 8.97 9.07 8.09 7.92 9.50 9.42 9.50 9.41 [Subtotal Other Components] (2) [11.43] [11.54] [11.73] [11.49] [9.50] [9.42] [9.50] [9.41] [sample] [Comparison 1] [2] [Comparison 3] [4] [5] [Comparison 6] [7] [Comparison 8] [Thickener] Claytone 40 1.77 0.83 0.96 0.99 0.88 1.73 0.61 1.28 EFKA®RM 1900 0.11 0.11 0.10 0.10 0.11 0.11 EFKA®RM 1920 0.22 0.17 0.19 0.11 0.31 [Subtotal] [Thickener] [2.10] [0.94] [1.23] [1.08] [0.99] [2.03] [0.72] [1.59] [Total Components] [100.00] [100.00] [100.00] [100.00] [100.00] [100.00] [100.00] [100.00] (1) The solvents thus added and the solvents from other ingredients and pigments (2) The concentrations of other components are based on dry mass. Solvents are listed separately.

[0123] The viscosities of the components in Table 1 were measured using a Brookfield viscometer with spindle #5 rotating at 10 rpm at 25°C, spindle #3 rotating at 0.5 and 20 rpm at 25°C, and spindle #2 rotating at 0.5 and 20 rpm at 25°C, using the method described above. The results are given in Tables 2, 3, and 4. As shown in Tables 3 and 4, according to the organic...

[0124] Solvent-based regressive reflective inks, coatings, or paints, as well as comparative compositions, exhibit shear-dilution behavior. Table 2: Brookfield viscosity using #5 spindles rotated at 10 rpm at approximately 25°C [sample] Viscosity [mPa] [s] [Comparison 1] 1800 [2] 840 [Comparison 3] 960 [4] 480 [5] 480 [Comparison 6] 1560 [7] 480 [Comparison 8] 6840

[0125] The Brookfield viscosity of the composition according to the invention, as measured using a #5 spindle rotating at 10 rpm, is therefore between 480 and 840 mPa·s, which is far lower than the value required for screen printing (ink) as disclosed in WO00 / 42113A1. Table 3: Brookfield viscosity at approximately 25°C using #3 spindle [sample] [at 0.5 rpm] [Lower viscosity [Pa·s]] [At 20 rpm] [Lower viscosity [mPa·s]] [Comparison 1] 12.24 860 [2] 1.44 378 [Comparison 3] 12.00 660 [4] 0.48 126 [5] 0.48 234 [Comparison 6] 10.80 930 [7] 1.20 348 [Comparison 8] 9.60 612

[0126] The Brookfield viscosity of the composition according to the invention, when measured using a #3 spindle rotating between 0.5 and 20 rpm, is therefore between 0.48 and 1.44 Pa·s and between 126 and 378 mPa·s, respectively, which are much lower than the lower values ​​specified in WO2004 / 017104A1. Table 4: Brookfield viscosity at approximately 25°C using #2 spindle [sample] [at 0.5 rpm] [Lower viscosity [Pa·s]] [At 20 rpm] [Lower viscosity [mPa·s]] [Comparison 1] 13.44 768 [2] 1.38 245 [Comparison 3] 12.54 633 [4] 0.30 138 [5] 0.84 213 [Comparison 6] 12.30 915 [7] 1.44 266 [Comparison 8] 38.52 Undetermined

[0127] The stability of the components in Table 1 is assessed by visual and tactile examination to determine whether the sample exhibits precipitation, condensation, or separation (phase or other forms) after a certain period of resuspension. See Table 5. Table 5 [sample] [4 hours after the final resuspension] [Sprayability] [48 hours after the final resuspension] [The sedimentation] [48 hours after the final resuspension] [Analysis] [Comparison 1] Sprayable none none [2] Sprayable none none [Comparison 3] Sprayable none none [4] Sprayable Very soft sediment none [5] Sprayable Very soft sediment none [Comparison 6] Sprayable none none [7] After slight shaking, it can be sprayed. Yes, possible re-floating Very few, possibly resuspended [Comparison 8] Sprayable Very soft sediment, may be resuspended Very few, possibly resuspended Example 2

[0128] Using a spray gun with a 1.3 mm nozzle (DeVILBISS HVLP, DV1-C1 Plus), the composition in Table 1 of Example 1 was applied to a flat gray metal test plate (10.5 x 14.9 cm, with an effective surface area of ​​154.2 cm²) with vertical black stripes (0.3 cm wide) spanning the entire surface. The spray gun was positioned 30 cm away from the metal test plate and a pressure of 1.9 bar was applied. One layer was applied. The layer was allowed to dry and cure in open air at approximately 20°C for 30 minutes. The weight of the applied dried and cured layer [g / m²] was determined (see Table 6). Table 6 [sample] [Weight of the dried and cured layer [g / m]] 2 , ] ] [Comparison 1] 138 [2] 151 [Comparison 3] 141 [4] 105 [5] 121 [Comparison 6] 146 [7] 174 [Comparison 8] 166

[0129] After drying, the coating quality is visually inspected. The general (non-central) reflexivity and maximum reflex angle [°] of both the comparative example and the example according to the present invention are considered good.

[0130] The maximum angle of recurrent reflection [°] was determined by guiding the torch beam to the recurrent reflection layer (where the line of sight to the eye substantially coincides with the torch beam) and visually confirming whether recurrent reflection was observed. The experiment began at zero angle relative to the coated substrate, and this angle was gradually increased until recurrent reflection could no longer be distinguished.

[0131] The smoothness or "orange peel" of a coating layer is assessed by guiding light through a grid at a certain angle to the surface of the coating layer and observing the sharpness of the grid image reflected from the surface of the coating layer. The sharper the grid image reflected from the surface of the coating layer, the smoother the surface and the less orange peel it has.

[0132] The results are presented in the following order in Figures 1a to 1h: Comparative Examples 1, 2, 3, 4 and 5, 6, 7, and 8. As can be clearly seen in Figures 1a to 1h, the examples according to the invention have a smoother surface than the corresponding comparative examples, i.e., fewer orange peel wrinkles. In this regard, the results of Comparative Example 1 (Figure 1a) are compared with those of Example 2 (Figure 1b), the results of Comparative Example 3 (Figure 1c) are compared with those of Example 4 (Figure 1d), Comparative Example 6 (Figure 1f) is compared with those of Example 5 (Figure 1e), and the results of Comparative Example 8 (Figure 1h) are compared with those of Example 7 (Figure 1g). The Brookfield viscosities obtained using the #2 spindle at approximately 25°C and 20 rpm according to the examples of the invention are all lower than those of the corresponding comparative examples.

[0133] none

[0134] Domestic storage information (please note in order of storage institution, date, and number) none Overseas storage information (please note in the order of storage country, institution, date, and number) none

Claims

1. An organic solvent-based relativistic composition selected from the group consisting of ink, paint, and coating compositions, having a first Brookfield viscosity η1 at a shear rate of 0.5 rpm between 0.2 and 8 Pa•s, and a second Brookfield viscosity η2 at a shear rate of 20 rpm between 80 and 450 mPa•s, provided that η2 is at least twice as low as η1, wherein, based on the total weight of the composition, the organic solvent-based relativistic ink, paint, or coating composition comprises: • 25-75 wt% organic solvent; • 1-74 wt% spherical glass beads having a median particle size D50 of 1-150 μm as measured by laser diffraction, and a refractive index of 1.5-2.8 as measured at a wavelength λ of 589 nm; • 0.15-1.2 wt% thickener; and • 0-30 wt% one or more other components; The Brookfield viscosities η1 and η2 were measured at 25°C using a #2 spindle in a 600 ml beaker with a diameter of 8.25 cm.

2. An organic solvent-based reflexive reflective composition selected from the group consisting of ink, paint, and coating compositions as described in claim 1, wherein, based on the total weight of the composition, the organic solvent-based reflexive reflective ink, paint, or coating composition comprises: • 25-68% by weight of an organic solvent; • 20-70% by weight of spherical glass beads having a median particle size D50 between 5 and 150 μm as measured by laser diffraction, and a refractive index between 1.5 and 2.8 as measured at a wavelength λ of 589 nm; • 0.15-1.2% by weight of a thickener; and • 0-30% by weight of one or more other components.

3. An organic solvent-based relativistic composition selected from the group consisting of inks, paints and coatings, as described in claim 1 or 2, wherein η1 is between 0.25 and 5 Pa•s and η2 is between 100 and 425 mPa•s, provided that η2 is at least twice as low as η1.

4. An organic solvent-based regressive reflective composition selected from the group consisting of inks, paints and coatings, as described in claim 1, having a fourth Brookfield viscosity η4 between 0.25 and 5 Pa•s at a shear rate of 0.5 rpm and a fifth Brookfield viscosity η5 between 80 and 450 mPa•s at a shear rate of 20 rpm, provided that η5 is at least twice as low as η4, as measured using a #3 spindle in a 600 ml beaker with a diameter of 8.25 cm at 25°C.

5. An organic solvent-based refractive reflective composition selected from the group consisting of inks, paints and coatings as described in claim 1, wherein the refractive index of the spherical glass beads, measured at a wavelength λ of 589 nm, is: (i) between 2.0 and 2.8; or (ii) between 1.7 and 2.

1.

6. An organic solvent-based regressive reflective composition selected from the group consisting of inks, paints and coatings as described in claim 1, wherein the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 1 and 100 μm.

7. An organic solvent-based regressive reflective composition selected from the group consisting of inks, paints and coatings as described in claim 1, wherein the median particle size D50 of the spherical glass beads, as measured by laser diffraction, is between 5 and 100 μm.

8. An organic solvent-based reflexive composition selected from the group consisting of inks, paints and coatings, as described in claim 1, wherein at least a portion of the spherical glass beads are coated with an aluminum-coated hemispherical layer.

9. An organic solvent-based reflexive composition selected from the group consisting of inks, paints and coatings, as described in claim 1, wherein the organic solvent is selected from the group consisting of aliphatic and aromatic solvents, ketones, esters, glycol ethers, alcohols, halogenated hydrocarbons and combinations thereof.

10. An organic solvent-based reflexive reflective composition selected from the group consisting of inks, paints and coatings as described in claim 1, wherein the thickener is selected from the group consisting of: (modified) hydrogenated castor oil, clay, modified clay, calcium sulfonate complexes, organophilic layered silicates, silicone, synthetic amorphous silica, acrylic gelling agents, modified cellulose materials, polyurea dispersions, urea-modified polyamide solutions, polyurethane dispersions, and combinations thereof.

11. An organic solvent-based reflexive composition selected from the group consisting of ink, paint and coating compositions as described in claim 1, wherein the composition contains 0.20-1.18% by weight of a thickener based on the total weight of the organic solvent-based reflexive composition selected from the group consisting of ink, paint and coating compositions.

12. An organic solvent-based relativistic composition selected from the group consisting of inks, paints and coatings as described in claim 1, wherein the one or more other components are selected from the group consisting of: foam control agents, luminescent agents, UV absorbers, adhesives and resins, preservatives, dyes and curing initiators.

13. A method for preparing an organic solvent-based reflexographic composition selected from the group consisting of inks, paints and coatings, according to any one of claims 1-12, the method comprising the steps of: (i) adding the organic solvent, the spherical glass beads, the thickener and one or more other components selected as appropriate to a container; and (ii) stirring or homogenizing the mixture obtained in step (i).

14. A method of coating a substrate with a reflexive reflective layer, the method comprising the steps of: a) providing a substrate; b) applying a primer layer to the substrate of step (a) as appropriate; c) applying a colored base layer to the substrate of step (a) or the primer layer of step (b) as appropriate; d) spraying an organic solvent-based reflexive reflective composition selected from the group consisting of inks, paints and coatings as described in any one of claims 1-12 onto the substrate of step (a) or the layer of step (b) or (c); e) drying and / or curing the substrate coated with the reflexive reflective layer obtained in step (d); and f) coating the dried substrate coated with the reflexive reflective layer obtained in step (e) with one or more additional transparent coating layers as appropriate, followed by drying and / or curing.

15. The method according to claim 14, wherein the organic solvent-based relativistic composition selected from the group consisting of inks, paints and coatings is applied to the substrate in step (d) by curtain coating, spraying with a spray gun, a high-speed rotating cup, a high-speed rotating disk or a spray can having a propellant.

16. The method according to claim 14 or 15, wherein step (d) includes n subsequent spraying steps to produce n layers, wherein layer x is at least partially applied to layer x-1, wherein x is an integer between 2 and n, and wherein n is an integer between 2 and 5.

17. A substrate coated with a reversion reflective layer, which can be obtained by the method described in any one of claims 14-16.

Images