Patent Description:
Color retention, which is defined by the color loss (or fading) of organic coatings on substrates arising from photodegradation, is highly desirable for exterior coatings. Premature and excessive fading typically occurs on surfaces with excessive exposure to sunlight, which can also exacerbate chalking of the coating. Color loss arises mechanistically from UV degradation, which accelerates chemical changes in the coloring agents by way of hydroxy and peroxy radical generation, which in turn lead to the onset of photo-oxidation (or photochemical degradation) in most polymers.

Color retention in pigmented coating formulations is especially challenging. TiO<NUM> pigment particles, which are invariably present in paints, while providing excellent hiding, strongly absorb UV radiation, leading to the formation of the oxidative hydroxyl radicals. Techniques used to mitigate the adverse effects of TiO<NUM> include pretreatment of the surface with SiO<NUM>, ZrO<NUM>, or both, which minimizes, but does not eliminate the formation of hydroxy radicals.

Attempts to mitigate the effects of UV light and TiO<NUM> on color loss in pigmented coatings include incorporating UV absorbers and antioxidants into paint formulations. These additives tend to have limited effectiveness over time; moreover, they tend to be more effective in reducing yellowing as contrasted with reducing color fading. Accordingly, it would be advantageous in the art of exterior coatings to find a simple, effective, and cost-efficient means of reducing color fading in pigmented coatings.

<CIT> discloses an invention that provides for new viscoelastic silicone rubbers and compositions and methods for making and using them. The invention provides for viscoelastic silicone rubbers that are stiffer on short timescales than they are on long timescales. When subjected to brief stresses, they are relatively stiff and elastic, and they resist changing shapes. When subjected to sustain stresses, however, they are relatively soft and accommodating, and they gradually change shapes. When those stresses are removed, they gradually return to their original shapes. These viscoelastic silicone rubbers resist compression set and they are extremely resilient in response to sudden impacts. They can be dense rubbers, foam rubbers, and particles.

<CIT> discloses that a silicone-based ink for additive manufacturing includes a vinyl-terminated diphenyl siloxane macromer, a treated silica hydrophobic reinforcing filler, a rheology modifying additive, and a plurality of porogen particles. A product of additive manufacturing with a silicone-based ink includes a plurality of continuous filaments arranged in a geometric pattern and a plurality of inter-filament pores, where the inter-filament pores are defined by the geometric pattern of the continuous filaments. Each of the continuous filaments includes a siloxane matrix having a plurality of intra-filament pores, where the intrafilament pores have an average diameter in a range of greater than <NUM> micron to less than <NUM>.

The present invention addresses a need in the art by providing, in one aspect, a method for forming a blend comprising an aqueous dispersion of polymer particles, a polymethylhydrosiloxane (PMHS), an opacifying pigment, and an extender; wherein the order of addition comprises the steps of either:.

The process of the present invention is useful for preparing pigmented paint formulations that exhibit excellent color retention when applied to substrates.

The present invention is a method for forming a blend comprising an aqueous dispersion of polymer particles, a PMHS, an opacifying pigment, and an extender; wherein the order of addition comprises the steps of either:.

The PMHS is preferably a homopolymer (m = <NUM>) or a copolymer where m > <NUM> and R<NUM> and R<NUM> are each independently CH<NUM>; in another embodiment, m is <NUM> to <NUM> and n is <NUM> to <NUM>. In a first aspect, the PMHS is blended in a first step with an aqueous dispersion of polymer particles (a latex), examples of which include polyacrylic, poly(styrene-acrylic), polyvinyl acetate, and polyurethane based latexes. In a second step, the PMHS/polymer particle blend is mixed with pigment and extender, either together or separately, and in any order. As used herein, "opacifying pigment" refers to a metal oxide having a refractive index of greater than <NUM>. Suitable opacifying pigments are TiO<NUM> and ZnO. Suitable extenders are carbonates, silica, silicates, aluminosilicates, phosphates, and non-hollow organic microspheres. More particular examples of extenders include talc, clay, mica, sericite, CaCO<NUM>, nepheline syenite, feldspar, wollastonite, kaolinite, dicalcium phosphate, and diatomaceous earth.

The concentration of the PMHS is preferably in the range of <NUM> to <NUM> weight percent, based on the weight of the blend (composition). The weight-to-weight ratio of the PMHS to the total of the opacifying pigment and the extender is preferably in the range of from <NUM>:<NUM>, more preferably from <NUM>:<NUM>, and most preferably from <NUM>:<NUM>, to <NUM>:<NUM>, more preferably to <NUM>:<NUM>, and most preferably to <NUM>:<NUM>. The preferred ratio of PMHS to opacifying pigment is in the range of from <NUM>:<NUM>, more preferably from <NUM>:<NUM>, and most preferably from <NUM>:<NUM>, to <NUM>:<NUM>, more preferably to <NUM>:<NUM>, and most preferably to <NUM>:<NUM>. TiO<NUM> is a preferred opacifying pigment.

In a second aspect, opacifying pigment is mixed with the aqueous dispersion of polymer particles to form an opacifying pigment/polymer particle blend, followed by mixing the opacifying pigment/polymer particle blend with the PMHS and the extender, either together or separately, and in any order.

In a third aspect, extender is mixed with the aqueous dispersion of polymer particles to form an extender/polymer particle blend; followed by mixing the extender/polymer particle blend with the PMHS and the opacifying pigment, either together or separately, and in any order.

In a fourth aspect, the PMHS is added to a blend comprising the aqueous dispersion of polymer particles, the pigment, and the extender. Significantly, the process of the present invention excludes contact of the PMHS with extender or pigment without the presence of the aqueous dispersion of polymer particles.

In another aspect, the total amounts of pigment and extender used in the process of the present invention are such that the composition has a pigment volume concentration (PVC) above a critical PVC. The term "critical pigment volume concentration" (CPVC) refers to the lowest concentration of polymer required to wet the surface of the pigment particles. Above CPVC, the volume of binder is insufficient to coat all pigment and extender. In a further aspect, the process of the present invention forms a composition with a PVC of at least <NUM>%, alternatively at least <NUM>% and, in one aspect, not greater than <NUM>%.

In yet another aspect, the total amounts of pigment and extender used in the process of the present invention are such that the composition has a pigment volume concentration (PVC) below a critical PVC. "Critical pigment volume concentration" (CPVC) refers to the lowest concentration of polymer required to wet the surface of the pigment particles. In this aspect, the process of the present invention forms a composition with a PVC not greater than <NUM>%, or not greater than <NUM>%, and, in one aspect, at least <NUM>%, or at least <NUM>%, or at least <NUM>%.

The CPVC of a coating can be conveniently determined using reflectance (integrated sphere, spectral reflectance included, <NUM> degree observer/D65), as follows: The difference in reflectance of a coated film in the dry state is compared to the same film that has been rewetted with a penetrating solvent that has refractive index similar to that of the polymer (such as Isopar L solvent) that fills the air voids of the dry coating. When a coating is above CPVC, the Y-reflectance of the re-wetted coating will decrease by at least <NUM>% from the initial Y-reflectance value of the dry coating. PVC is defined by the following formula: <MAT> where binder solids refers to the contribution of polymer from the aqueous dispersion of the polymer particles that bind the pigment and extender particles together.

The process of the present invention preferably further includes the addition of any or all of solvents, rheology modifiers, defoamers, dispersants, preservatives, coalescents, neutralizing agents, colorants, and additional water. The preferred order of addition of these materials is readily determined by those of ordinary skill in the art without undue experimentation.

It has been surprisingly been discovered that exterior paints prepared using the process of the present invention provide coatings with exceptional color retention when subjected to accelerated UV exposure.

Above-critical paint formulations were prepared in accordance with Table <NUM>. In the table, PRIMAL™ WDV-<NUM> refers to PRIMAL™ WDV-<NUM> Acrylic Copolymer (<NUM>% solids); METHOCEL™ J75MS refers to METHOCEL™ J75MS Cellulose Ether; Nopco NXZ refers to Nopco NXZ Defoamer; Calgon N refers to Calgon N (<NUM>%) Dispersant; TAMOL™ 165A refers to TAMOL™ 165A Dispersant (<NUM>%); Ti-Pure R-<NUM> refers to Ti-Pure R-<NUM> TiO<NUM>; Attagel <NUM> refers to Attagel <NUM> Attapulgite; Minex <NUM> refers to Minex <NUM> Nepheline syenite extender; Durcal (Omyacarb <NUM>) refers to Durcal (Omyacarb <NUM>) CaCO<NUM>; Durcal (Omyacarb <NUM>) refers to Durcal (Omyacarb <NUM>) CaCO<NUM>; Temisca #<NUM> refers to Temisca #<NUM> sand; Unimin <NUM>-<NUM> refers to Unimin <NUM>-<NUM> sand; Rozone <NUM> refers to Rozone <NUM> Preservative; DOWANOL™ refers to DOWANOL™ DPnB Coalescent; PMHS/PDMS refers to the polymethylhydrosiloxanes/polydimethyl siloxane polymers illustrated in Table <NUM>. PRIMAL, METHOCEL, TAMOL, and DOWANOL are all Trademarks of The Dow Chemical Company or Its Affiliates.

Five PMHS and one PDMS siloxane polymers were added to the paint formulations at <NUM> weight percent based on the weight of the formulations. The polymers are summarized in Table <NUM>:.

The paint formulations were pigmented with Colortrend Blue <NUM>-<NUM> dye (<NUM> wt%) and applied to an aluminum panel (<NUM> thickness). The coated panels were allowed to dry at <NUM> at <NUM>% relative humidity, then subjected to accelerated UV exposure for <NUM> using a Ci <NUM> xenon arc Weather-O-Meter (Atlas Corp. ) set at ASTM G-<NUM> cycle <NUM> (<NUM> daylight followed by <NUM> water spray on the coated surface. ) The radiance was set at <NUM> W/m<NUM>.

ΔE was measured using a Byk-Gardner Spectro-Guide Colorimeter in accordance with ASTM D-<NUM>. The greater the ΔE, the poorer the color retention. In general a ΔE of greater than <NUM> is perceptible to the human eye. Table <NUM> illustrates the color retention (ΔE) at <NUM> for coatings formed from the above-critical paint formulations (PVC = <NUM>) containing no polysiloxane additive, a PMHS additives <NUM>-<NUM>, and the PDMS additive.

Table <NUM> illustrates the components and amounts of a below-critical paint formulation. In the following table, Rocima <NUM> refers to Rocima <NUM> Microbicide; TERGITOL™ <NUM>-S-<NUM> refers to TERGITOL™ <NUM>-s-<NUM> Secondary Alcohol Ethoxylate; Bioban IPBC <NUM>-LE refers to Bioban IPBC <NUM>-LE Antimicrobial; Foamstar A-<NUM> refers to Foamstar A-<NUM> Defoamer; RHOPLEX™ VSR-<NUM> refers to RHOPLEX™ VSR-<NUM> Acrylic Latex; ACRYSOL™ RM-8W and ACRYSOL™ RM-<NUM> NPR refer to ACRYSOL™ RM-8W and ACRYSOL™ RM-<NUM> NPR Rheology Modifier. TERGITOL, RHOPLEX, and ACRYSOL are all Trademarks of The Dow Chemical Company or Its Affiliates.

The paint formulations were pigmented with Colortrend Blue <NUM>-<NUM> dye (<NUM> wt%) and applied to an aluminum panel (<NUM> thickness). The accelerated UV testing was carried out as described hereinabove.

Table <NUM> illustrates the color retention (ΔE) at accelerated UV exposure for <NUM> for coatings formed from below-critical paint formulations (PVC = <NUM>) containing no polysiloxane additive (Comparative Example <NUM>) and PMHS <NUM> at <NUM> weight percent based on the weight of the formulation of Table <NUM> (Example <NUM>).

Claim 1:
A method for forming a blend comprising an aqueous dispersion of polymer particles, a polymethylhydrosiloxane (PMHS), an opacifying pigment, and an extender; wherein the order of addition comprises the steps of either:
a) mixing the PMHS with the aqueous dispersion of polymer particles to form a polymethylhydrogensiloxane/polymer particle blend; then mixing the polymethylhydrogensiloxane/polymer particle blend with the opacifying pigment and the extender in any order; or
b) mixing the opacifying pigment with the aqueous dispersion of polymer particles to form an opacifying pigment/polymer particle blend; then mixing the opacifying pigment/polymer particle blend with PMHS and the extender in any order; or
c) mixing the extender with the aqueous dispersion of polymer particles to form an extender/polymer particle blend; then mixing the extender/polymer particle blend with PMHS and the opacifying pigment in any order; or
d) adding the polymethylhydrogensiloxane to a blend comprising the aqueous dispersion of polymer particles, the pigment, and the extender;
wherein the PMHS is represented by the following formula:
<CHM>
where each R<NUM> is independently H or SiMe<NUM>; R<NUM> is CH<NUM> or phenyl; and R<NUM> is C<NUM>-C<NUM>-alkyl, C<NUM>-C<NUM>-alkoxy, or phenyl; m is from <NUM> to <NUM> and n is from <NUM> to <NUM>;
wherein the opacifying pigment is TiO<NUM> or ZnO;
wherein the extender is a carbonate, silica, silicate, aluminosilicate, phosphate, non-hollow organic microspheres, talc, clay, mica, sericite, CaCO<NUM>, nepheline, feldspar, wollastonite, kaolinite, dicalcium phosphate, or diatomaceous earth;
and wherein the aqueous dispersion of polymer particles is selected from polyacrylic, poly(styrene-acrylic), polyvinyl acetate and polyurethane based latexes.