Patent Grant
8163078
The present invention is generally related to controlling pigment spacing in a coating composition. More particularly, the present invention is related to achieving an improved TiO2 spacing in a paint, such as by using nanoparticles of ZnO, SiO2, or Al2O3 of differing size and density distribution.
Pigments such as titanium dioxide are a common component of coating compositions, particularly paint. Paint generally comprises a film-forming material or binder, a pigment, and a carrier or solvent which evaporates to leave the solids as a coating on a substrate.
The pigment is generally partially or wholly suspended or dissolved in the carrier. Film formation of paint occurs when the paint is applied to a substrate and the carrier evaporates. During this process, the particles of pigment and binder come closer together. As the last vestiges of liquid evaporate, capillary action draws the binder particles together with great force, causing them to fuse and bind the pigment into a continuous film. This process is often referred to as coalescence.
Thus, the spacing and orientation in the carrier of the pigment particles relative to each other, and the various other solids, is essentially retained when the solid film is formed on the substrate. Flocculation and settling of the pigment phase are particularly undesirable. The pigments tend to cling together as packed pigment particles by agglomerating or clustering and then tend to resist subsequent redispersion by agitation, thus degrading the hiding power of the resulting paint. Hiding power is among one of the most important attributes of paint, and hiding power is determined particularly in white paint by the light scattering effectiveness of the pigment. The light scattering effectiveness of the pigment is in turn highly dependent on the spacing arrangement of the pigment in the dried coating as well as the particle sizes. Many different methods are known in the art for affecting and controlling the sizes of the pigment particles; however, this has proven to be ineffective in controlling light scattering sufficiently.
The pigment which is most widely used in paint is titanium dioxide. However, titanium dioxide is relatively expensive in comparison to the costs of other components used in paint. As such, there is a need to maximize the beneficial aspects of titanium dioxide, while minimizing the amount used. Enhanced light scattering occurs when the titanium dioxide pigment particles have a diameter of about 200 to 300 nm and are uniformly spaced about the same distance apart. Most commonly, particulate TiO2 in the range of 100 nm to 400 nm is utilized in conventional paint.
Various techniques have been attempted and used in the art to promote an even spacing and distribution of the pigment in the coating. A number of pigments have been found to function as “extender” pigments, wherein the extended pigments are alleged to function in mechanically spacing the opacifying or “prime” pigments. However, the flocculation forces present during the drying of paint still result in the presence of clusters and flocs of pigment particles. Thus, even if total deaggregation is accomplished in the dispersion process, a random distribution of pigment particles will not approach the theoretical optimum that an ideally spaced distribution would achieve.
Regardless of the technique, prior art coatings do not achieve a level of opacity which approaches that predicted theoretically. Thus, there is a long felt need for further improvement, such as a more efficient packing arrangement of TiO2 particles in a coating formed on a substrate.
The present invention provides methods and compositions for coatings wherein the TiO2 particles exhibit improved spacing over conventional paint formulations. Without limiting the scope of the invention, it is believed that the nanoparticle-sized pigment particles (specifically nano-ZnO) have an affinity for the surface of pigmentary TiO2 particles. It is therefore believed that the nano ZnO particles effectively are disposed around and associated with the TiO2 particle so that the efficiency of the TiO2 particles arrangement increases; i.e., the overall stability of TiO2 pigment particles on drying is improved, thus improving properties such as tint strength and hiding power (contrast ratio). It is believed that the nano ZnO particles are interacting with the TiO2 to form a more efficient dispersion.
In one embodiment, a method is provided for producing a titanium dioxide particle dispersion having nano-particle pigments interacting with the titanium dioxide to provide for more efficient packing arrangement of the titanium dioxide. In a preferred embodiment, the present invention relates to a paint composition of titanium dioxide, and a nanoparticle pigment, such as ZnO, and also a binder and a dispersant, along with additives as known in the art for formulating paint. The nanoscale zinc oxide, silicone dioxide, and aluminum oxide provide for a more uniform dispersment of the titanium dioxide when the paint dries to form a coating on a substrate.
It is known that efficient spacing of TiO2 particles in a paint produces a paint that has improved tint strength and hiding power. However, in most paints, upon drying, the TiO2 pigment particles agglomerate and thus reduce the efficiency of the TiO2 particles. This agglomeration of TiO2 particles yields paints that have lower tint strength and hiding power.
It is believed in accordance with the principles of the present invention that the nanoparticle-sized pigment particles (specifically nano-ZnO) are uniformly distributed within the paint matrix. Through this uniform distribution of particles, higher tint strength and hiding power are observed. This uniform distribution is achieved through the interaction of the surface modified/treated of the TiO2 (as supplied by the TiO2 manufacturer) and nano particles. The TiO2 used in the paint has metal oxide surface treatment along with oligomeric/polymeric dispersant; which keeps the TiO2 particles from flocculating to a certain extent in the dry film. Addition of surface treated nano particles (treated in house with an oligomeric/polymeric dispersant) further enhances the spacing of TiO2. Typically, addition of untreated nano particles (ex. ZnO) to a paint would flocculate the TiO2 and make the paint useless. However, with the proper pretreatment of both TiO2 and nano particles, electro-steric interactions prevent flocculation from occurring in the wet paint and during the paint drying process. By preventing the particles from flocculating, optimal TiO2 spacing is achieved. Although prior art has shown some TiO2 spacing with extender pigments, none has been known to produce as effective results.
The ideal spacing of TiO2 is illustrated in
The positive attributes of nano ZnO particles in paints is resin system dependent, especially for tint strength and gloss observations. Thus, various resin systems can be used as known in the art. The most profound and preferred results are seen with acrylic resin systems (both self-crosslinking and non self-crosslinking). Contrast ratio increases are observed for all types of resin systems.
Similarly, various pigmentary TiO2 particles respond differently to the addition of nano ZnO particles. Thus, various pigmentary TiO2 particles can be used in accordance with the principles of the present invention. Commercial sample 1, a TiO2 product sold under the trade name Kronos 4311 by KRONOS Worldwide, Inc., located at 16825 Northcase Drive, Suite 1200, Houston, Tex. 77210-4272, responds well in terms of tint strength and contrast ratio and is a preferred component. Commercial sample 3, sold under the trade name Tiona RCS-2 by Millennium Chemicals, Inc., located at 20 Wright Avenue, Suite 100, Hunt Valley, MD. 21030, performs similarly, but it is not as efficient. Commercial sample 2, sold under the trade name Tiona 596S, also by Millennium Chemicals, Inc., located at 20 Wright Avenue, Suite 100, Hunt Valley, MD. 21030, has only minimal improvements when compared to Commercial sample 1 and Commercial sample 3.
A master batch of paint prepared in accordance with the principles of the present invention was made holding a portion of water. The batch was then apportioned, and the proper amounts of nanoparticles (see examples below) and water were post-added. Various components of the paint were varied depending on the focus of the experiment. Tint strength and contrast ratio of each sample were evaluated. Tables 1A-G list the basic formulation for Paints A-G, respectively.
Table 1.
The following nanoparticles were screened in a typical paint formulation: Al2O3, SiO2, and ZnO (two particle sizes) at two concentration levels, 0.50% and 1.00%. Particle sizes of these nanopigments ranged from ˜10-120 nm. TABLE 2 shows the data for the nanoparticle screening tests. The starting Paint A is any conventional white base paint with a PVC of ˜23.0. The concentration of nanoparticles is a percentage based on the total formula weight.
Three observations are noted from TABLE 2 first, all of the different nanoparticles studied yield an increase in tint strength and contrast ratio when formulated into Paint A (as opposed to Paint A without nanopigmentation). Second, improved tint strength and contrast ratio are observed with various particles sizes (˜10-120 nm). Lastly, increasing the concentration of nanoparticles (0.5% vs. 1.0%) yields an increase in tint strength and contrast ratio. From this screening study, Paint A with added nano ZnO (˜60 nm particle size) at a concentration of 0.5% yielded the highest increase in tint strength (28.75%) and contrast ratio (0.75%). One skilled the art would appreciate that while the contrast ratio increase is small, a mere increase of 0.40% will show a noticeable visual improvement in hiding power.
In this study, the concentration range of nano ZnO (˜60 nm particle size) was examined in Paint A. The concentrations of nano ZnO examined were 0.05%, 0.10%, 0.25%, 0.50%, 1.00%, 1.50%, 2.50%, and 5.00%. TABLE 3 shows the tint strength and contrast ratio data for increasing the nano ZnO concentration in Paint A. The concentration of nano ZnO is expressed as a percentage based on total formula weight.
The data in TABLE 3 illustrate that as the concentration of nano ZnO (particle size of ˜60 nm) is increased in the base Paint A (0.05-5.00%), the tint strength and contrast ratio increase (as opposed to Paint A without nanopigmentation). The optimum use level of nano ZnO (particle size ˜60 nm) is 0.50%, yielding a tint strength increase of 28.75% and a contrast ratio of 0.75%.
This study examines the effect of blending nanoparticles of different composition and different particle sizes into a typical base paint formulation (Paint B in this case). The nanoparticles studied were ZnO (˜60 nm and ˜120 nm particle size) and Al2O3 (·50 nm particle size). TABLE 4 lists the contrast ratio results for Paint B with various added blends of nanopigmentation. The nanoparticles are examined alone, and then as the blends listed in TABLE 4. The concentration for each of the different nanoparticles was 0.50% based on total formula weight. The base Paint B is a conventional, well known paint with a PVC of ˜28.0.
TABLE 4 illustrates that when the nanoparticles are used alone or in blends of equal ratios in base Paint B, contrast ratio is increased (opposed to Paint B without nanopigmentation). This increase in contrast ratio is noted in all of the listed cases, whether the nanopigments are of approximately equal size (nano ZnO, ˜60 nm blended with nano Al2O3, ˜50 nm) or are of different sizes (either nano ZnO, ˜60 nm blended with nano ZnO, ˜120 nm or nano Al2O3, ˜50 nm blended with nano ZnO, ˜120 nm). In this study, the largest improvement in contrast ratio was observed, 0.55%, with the combination of the base Paint B with a blend of nano ZnO (˜120 nm) and nano Al2O3 (˜50 nm).
The following example demonstrates that the most common resin systems typically used in architectural coatings can be used with the nanotechnology described in this patent. The resin systems that were examined in this study were two acrylic resins (one self-crosslinking, one non self-crosslinking), a styrene-acrylic resin, a polyvinyl acrylic (PVA), and a vinyl acetate ethylene (VAE) resin. These commercially available resins were used to make up several conventional base paints as set forth in Table 1, Paint A (23.0 PVC), Paint B (28.0 PVC), Paint C (23.0 PVC), Paint D (51.75 PVC), and Paint E (27.64 PVC). All of these paints were examined with and without 0.50% (based on total formula weight) of nano ZnO (˜60 nm particle size). TABLE 5 lists the tint strength and contrast ratio results for Paints A-E.
The data in TABLE 5 illustrates that the effect of spacing with nanoparticles (ZnO ˜60 nm in this case) is observed in paints made with different resin compositions. All of the various resin types, acrylic (self-crosslinking), acrylic (non self-crosslinking), styrene-acrylic, PVA, and VAE in Paints A-E all show an improvement in tint strength and contrast ratio (over Paints A-E without nanopigmentation). The most dramatic improvement in tint strength and contrast ratio is observed with additions to base Paint A, which was formulated with a 100% self-crosslinking acrylic resin. Paint A, as modified, shows a 28.75% increase in tint strength and a 0.75% increase in contrast ratio.
This study examines several different commercially available pigmentary TiO2 types and their ability to be spaced with nanoparticles (ZnO, ˜60 nm particle size in this case) as described in this patent. Three different pigmentary TiO2 products were studied as additives in base Paint A, with and without nanopigmentation (0.50% ZnO, based on total formula weight). The three different TiO2 products studied were Commercial-1, Commercial-2, and Commercial-3 previously described. TABLE 6 lists tint strength and contrast ratio data for these Paints.
The data in TABLE 6 illustrates that an improvement in tint strength and contrast ratio is observed in base Paint A, as modified, with all three commercially available pigmentary TiO2 types. The largest improvement is noted in modified Paint A with TiO2 type Commercial-1, showing an increase in tint strength of 28.75% and contrast ratio increase of 0.75%.
This example demonstrates that nanoparticles (ZnO, ˜60 nm in this case) can be used to effectively space various levels of pigmentary TiO2 in a typical architectural coatings formulation. Paint A was studied with various added levels of Commercial-1 TiO2; 7.10%, 10.70%, 14.20%, 17.80%, 21.10%, 24.90%, and 28.50% (based on total formula weight) with and without nanopigmentation (0.50% of nano ZnO, ˜60 nm). TABLE 6 lists the tint strength and contrast ratio data for these paints.
TABLE 7 illustrates that at every level of pigmentary TiO2 examined, an improvement in tint strength and contrast ratio is observed (as compared to the corresponding paint without nanopigmentation). The largest increase in tint strength and contrast ratio is observed with modified Paint A having 24.90% TiO2 (based on total formula weight) with 0.50% ˜60 nm nano ZnO (based on total formula weight); this paint shows a 29.25% increase in tint strength and a 0.90% increase in contrast ratio.
This example demonstrates that nanoparticles (ZnO, ˜60 nm in this case) can be used to effectively space pigmentary TiO2 in typical architectural paints of varying PVC. Paints of three different PVC's were examined in this study (all with the same resin and TiO2 types) at PVC's ranging from ˜28.0-50.50 PVC. TABLE 8 lists the tint strength and contrast ratio improvements for these three paints.
TABLE 8 illustrates that for the PVC range of ˜28.0-50.50 PVC, an improvement in tint strength and contrast ratio is noted. The best improvement in this particular study was with modified Paint B (28.10 PVC) with tint strength improved by 5.50% and contrast ratio improved by 0.40%.
This application is a continuation of U.S. patent application Ser. No. 12/346,407, filed on Dec. 30, 2008, now U.S. Pat. No. 7,727,323, which is a continuation of U.S. patent application Ser. No. 10/914,594 filed on Aug. 9, 2004, now U.S. Pat. No. 7,482,054. Both applications are incorporated herein by reference in their entirety.
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