Background of the Invention

Latex binders that adsorb to Ti0 ₂ are known to form composites with Ti0 ₂ , leading to greater pigment efficiency in paint films. It is possible to use the adsorbing polymer as a portion of the binder in the paint (pre-composite) to maximize hiding and to use a second non adsorbing (let-down) binder to achieve other desired properties and to reduce cost. One of the problems often observed with current pre-composite technology is formation grit occurring during the preparation of the composite arising from the uncontrolled reaction of the pre-composite with Ti0 ₂ . To control grit, the formulator must carefully mix the adsorptive latex with the pigment under controlled conditions to avoid flocculation, which often requires expensive high shear mixing. It would, therefore, be an advantage to reduce grit formation in formulations that include latex binder and Ti0 ₂ in a controlled and cost-effective manner.

Summary of the Invention

The present invention addresses a need in the art by providing a process comprising the steps of a) contacting an aqueous dispersion of a Ti0 ₂ slurry containing adsorbing dispersant with an adsorbing latex to form a mixture, wherein the pH of the mixture of the Ti0 ₂ slurry and adsorbing latex are sufficiently high to inhibit interaction between the Ti0 ₂ and the adsorbing latex; then b) lowering the pH of the mixture of step a) sufficiently to promote interaction between the Ti0 ₂ and the adsorbing latex, thereby forming a composite. The process of the present invention provides for better hiding and reduced grit for coatings compositions.

Detailed Description of the Invention

The present invention is a process comprising the steps of a) contacting an aqueous dispersion of a Ti0 ₂ slurry containing adsorbing dispersant with an adsorbing latex, wherein the pH of the mixture of the Ti0 ₂ slurry and the adsorbing latex are sufficiently high to inhibit interaction between the Ti0 ₂ and the adsorbing latex; then b) lowering the pH of the composition of step a) sufficiently to promote interaction between the Ti0 ₂ and the adsorbing latex, thereby forming a composite.

In the first step, an aqueous dispersion of Ti0 ₂ and the dispersant (Ti0 ₂ slurry) are contacted with an adsorbing latex (also referred to as pre-composite). The pH of the Ti0 ₂ slurry is pre-adjusted with a suitable base from its nominal level, typically from about 8 to 9, to a level sufficiently high to inhibit interaction between the Ti0 ₂ and the subsequently added adsorbing latex. Preferably, the pH is raised to from about 10 to about 12. The pH of the mixture is advantageously maintained for a sufficient time to remove from 30 to 50% of the dispersant adsorbed on the surface of the Ti0 ₂ particles; depending on the nature of the dispersant and the surface properties of the Ti0 ₂ , this delay time is generally in the range of from about 10 minutes to about 24 h. After a suitable delay time, the pH is then lowered back to a desired level, generally to between 8.5 and 9.

The pH of the adsorbing latex is also at or raised to a level so that the latex, when contacted with the Ti0 ₂ slurry, results in a mixture having a pH sufficiently high to inhibit interaction between the Ti0 ₂ and the adsorbing latex. Thus, for example, an adsorbing latex at pH -10 can be mixed with a Ti0 ₂ slurry at pH -10 to achieve the desired affect; it is also possible to achieve the same result by mixing an adsorbing latex having a relatively low pH (-8.5) with a Ti0 ₂ slurry having a relatively high pH (-12), so long as the resulting mixture has a pH sufficiently high to inhibit interaction between the Ti0 ₂ particles and the adsorbing latex.

The base used to raise the pH can be organic or inorganic. Examples of suitable organic bases include alkanol amines such as 2-amino-2-methyl-l-propanol and 2-amino-2-ethyl-l,3-propane-diol; examples of suitable inorganic bases include alkali metal and alkaline earth hydroxides and carbonates such as NaOH, KOH, and Na ₂ C0 ₃ . Ammonia is also a suitable base.

Suitable pre-composites include acrylic, styrene-acrylic, vinyl ester, and ethylene-vinyl ester containing latexes. Acrylic latexes preferably contain structural units of (meth)acrylates such as methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, and ethyl hexyl acrylate and combinations thereof. Preferred vinyl ester latexes are vinyl acetate latexes; preferred vinyl ester-ethylene latexes are vinyl acetate-ethylene latexes.

As used herein, the term "structural units" is used to refer to the groups formed from the polymerization of the corresponding monomer. Thus, a structural unit of methyl methacrylate is as illustrated:

where the dotted lines indicate the points of connectivity to the polymer backbone. The pre-composite further includes an adsorbing moiety, which is a functional group pendant to the polymer backbone that adsorbs to the surface of the Ti0 ₂ particles. It is understood that Ti0 ₂ particles may be surface treated with metal oxides such as alumina, silica, and zirconia oxides and combinations thereof. Thus, the adsorptivity of the surface of the Ti0 ₂ particles varies with the nature of the surface treatment.

Typically, the adsorbing moiety includes structural units of an acid monomer, such as a phosphorus acid- containing monomer at a concentration preferably in the range of from 0.1 to 5 weight percent, based on the weight of the pre-composite. Examples of suitable phosphorus acid monomers include phosphonates and dihydrogen phosphate esters of an alcohol in which the alcohol contains or is substituted with a polymerizable vinyl or olefinic group. Preferred dihydrogen phosphate esters are phosphates of hydroxyalkyl(meth)acrylates, including phosphoethyl methacrylate and phosphopropyl methacrylate, with phosphoethyl methacrylate being especially preferred.

Ti0 ₂ is generally supplied as a powder, which is rendered into an aqueous dispersion, or as an aqueous slurry. In either case, a dispersant, which adsorbs to the surface of the Ti0 ₂ , is generally used to stabilize the pigment particles. The adsorbed particles disadvantageously prevent adsorption of adsorbing latex particles (pre-composite particles) that are blended with the slurry to improve hiding efficiency.

An increase in pH appears to provide a mechanism for removing dispersant from the surface of the Ti0 ₂ particles where dispersant removal is desired. Thus, when the latex is added to the high pH slurry, the latex particles can out-compete the dispersant for adsorption to the surface of the Ti0 ₂ particles once the pH is lowered sufficiently to promote adsorption; this phenomenon occurs because the latex particles have a greater affinity than the dispersant for the Ti0 ₂ . The pH can be lowered with a suitable acid, for example citric acid; however, if the base used to raise the pH is volatile (e.g., ammonia), it would be possible to lower pH with an acid or by allowing the base to evaporate or boil off.

Additionally, in a system where latex reactivity is not inhibited by dispersant, raising pH followed by adsorbing latex addition followed by lowering pH can be advantageous, especially in a system with very reactive pigment and latex. In the absence of "turning off' the reaction mechanism by raising pH, these especially reactive latexes and pigments can react with each other uncontrollably with the consequence of forming undesirable levels of grit. Using the processes described in the prior art, extreme care is generally required to control the rates of addition and mixing of the highly reactive pigment and latex to offset the detrimental effects of their reactivity. Using the process of the present invention whereby reactivity is turned off at high pH and turned on at low pH allows for a controlled reaction that results in the dramatic reduction of grit.

The composite prepared by the process of the present invention can be formulated with any of a number of suitable components to make a coating composition such as a paint, including solvents; fillers; pigments, such as titanium dioxide, mica, calcium carbonate, silica, zinc oxide, milled glass, aluminum trihydrate, talc, antimony trioxide, fly ash, and clay; polymer encapsulated pigments, such as polymer-encapsulated or partially encapsulated pigment particles such as titanium dioxide, zinc oxide, or lithopone particles; polymers or polymer emulsions adsorbing or bonding to the surface of pigments such as titanium dioxide; hollow pigments, including pigments having one or more voids; dispersants, such as aminoalcohols and polycarboxylates; surfactants; defoamers; preservatives, such as biocides, mildewcides, fungicides, algaecides, and combinations thereof; flow agents; leveling agents; and additional neutralizing agents, such as hydroxides, amines, ammonia, and carbonates.

For example, the coatings composition may include polymer-encapsulated opacifying pigment particles comprising i) opacifying pigment particles, such as titanium dioxide particles, having a diameter in the range of 100 nm to 500 nm and an index of refraction of at least 1.8; ii) an encapsulating polymer, and iii) a polymeric dispersant for the encapsulated opacifying pigment particles and the polymer. Such polymer- encapsulated opacifying pigment particles are described, for example, in U.S. Patent Publication US 2010/0298483 Al . In another example, the coating composition may include polymer-encapsulated opacifying pigment particles as described in WO 2007/112503A1.

Examples

The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example 1 - Preparation of a Ti0 ₂ Slurry, Composite, and Paint Formulation

A Ti0 ₂ slurry was prepared by first adding TAMOL™ 851 Dispersant (A Trademark of The Dow Chemical Company or its Affiliates, 16.04 g) to water (558.96 g) and mixing at low speed. Tronox CR- 826 grade Ti0 ₂ powder (1925.0 g) was added slowly to the aqueous dispersant using a Cowles disperser. Once the pigment was fully incorporated, the disperser was set to 1800 to 2000 rpm for 20 min. This slurry was stored on a roller mill for at least 24 h before the next step.

A portion of the slurry (1 12.47 g) was then adjusted to pH 10 with AMP™-95 2-Amino-2-methyl-l- propanol (A Trademark of The Dow Chemical Company or its Affiliates, 0.46 g). The slurry was held at H 10 overnight (-18 h), after which time the slurry was added to a mixture of the pre-composite polymer (115.29 g, pH = 7.9) Foamstar A-34 defoamer (0.40 g), and water (20.02 g) with mixing speed of 450 rpm. The slurry/pre-composite mixture was then neutralized with citric acid (0.40 g) and diluted with water (9.75 g) to form a composite.

A portion of the composite (161.76 g) was added with mixing to a separate vessel containing RHOPLEX™ VSR-1050LOE Acrylic Emulsion (A Trademark of The Dow Chemical Company or its Affiliates, 47.68 g). Extender grind was then added to the vessel, followed by letdown, each prepared by mixing the ingredients shown in Table 1, in the amounts and in the order shown, to make the paint (208 mL). The paint was equilibrated overnight and found to have an S/mil of 6.92 by ASTM Test Method D-2805.70. Examples 2 and 3 were prepared by the procedure described for Example 1 except that the pH was adjusted to 10.5 for Example 2 and to 11 for Example 3.

Comparative Example 1 was prepared substantially as described for Example 1 except that the pH of the Ti0 ₂ slurry for the comparator was not adjusted with base from as-supplied level of 8.5. The pH of the comparator readjusted to 8.87 with AMP™-95 2-Amino-2-methyl-l-propanol for the paint formulation.

Table 1 shows the recipes for the ingredients used to make paints for the Comparative Example and Examples 1 - 3. The pre-composite polymer for Examples 1 - 3 is 46 weight percent, based on the weight of water and the polymer; by weight, the pre-composite polymer is 54.0 % butyl acrylate / 43.0 % methyl methacry late/ 1.5 % phosphoethyl methacrylate/ 0.2 % methacrylic acid/0.5% ureido methacrylate, and further includes TAMOL™ 2002 APEO free Emulsion Dispersant (A Trademark of The Dow Chemical Company, 0.9 weight % based on the weight of dispersant solids and the pre-composite polymer solids).

Comp. Ex Ex. 1 Ex. 2 Ex. 3

Ingredients ( ) 8.5 pH 10.0 pH 10.5 pH 11.0 pH

RHOPLEX™ VSR-1050LOE 47.68 47.68 47.68 47.68

Acrylic Polymer Emulsion

Composite Stage

Pre-Composite Polymer 72.06 72.06 72.06 72.06

Foamstar A-34 Defoamer 0.25 0.25 0.25 0.25

Water 12.50 12.51 12.51 11.25

Ti02 Slurry Premix

Tronox CR-826 + Tamol 851 Ti02 Slurry 70.29 70.29 70.29 70.29

AMP™-95 2-Amino-2-methyl- 1 -propanol 0.09 0.29 0.51 1.17

Post-Premix Composite

10% Citric Acid 0.00 0.25 1.54 5.25

AMP™-95 2-Amino-2-methyl-l -propanol 0.08 0.00 0.00 0.00

Water 6.49 6.09 4.57 1.41

Composite Total 161.76 161.75 161.73 161.68

Extender Grind

Water 2.25 2.25 2.25 2.25

TAMOL™ 165 A dispersant 0.11 0.11 0.11 0.11

BYK 348 Surfactant 0.50 0.50 0.50 0.50

Foamstar A-34 Defoamer 0.50 0.50 0.50 0.50

Minex 10 Extender 4.41 4.41 4.41 4.41

Water 0.75 0.75 0.75 0.75

Grind Total 8.52 8.52 8.52 8.52

Letdown

ROPAQUE™ Ultra E pigment 11.23 11.23 11.23 11.23

Optifilm Enhancer 400 Coales. Aid 1.81 1.81 1.81 1.81

Potassium Hydroxide 5% 0.65 0.65 0.65 0.65

ACRYSOL™ RM-2020 NPR Thickener 7.70 7.70 7.70 7.70

Water 18.14 18.14 18.14 18.14

ACRYSOL™ RM-8W Thickener 1.33 1.33 1.33 1.33

Total 257.47 257.46 257.44 257.39

All noted trademarks are owned by The Dow Chemical Company or Affiliates thereof.

Table 2 shows the effect on hiding of increasing pH to the range of 10-11, then lowering pH. Table 2 - Effect of Increasing and Decreasing pH on Hiding

Comp. Ex. 1 Ex. 1 Ex. 2 Ex. 3

Ti0 ₂ Slurry pH 8.5 10 10.5 11

Properties

pH - Paint Formulation 8.87 8.97 8.95 8.87

S/mil 6.55 6.92 7.01 7.08

The process of the present invention allows paint formulators to use grades of Ti0 ₂ with varying degrees of reactivity for a given pre-composite; thus, the formulator no longer needs to tailor the reactivity of the pre-composite to the reactivity of the Ti0 ₂ .

Example 4 and Comparative Example 2 - Grit Formation of Drawndown Samples

The pre-composite used for Example 4 and the Comparative Example 2 is the same as for Examples 1 -3 except that it contains no TAMOL™ 2002 APEO free Emulsion Dispersant.

Comparative Example 2

Kronos 4311 Ti0 ₂ pigment slurry (69.5 g, pH = 8.5) was added with stirring into a mixture of the pre- composite (69.14 g, pH = 7.9), water (22.2 g) and defoamer (0.25 g). The mixture, which had a 36% volume solids and a pigment volume concentration (PVC) of 31.7%, was drawn down into a film, whereupon grit was immediately observed.

Example 4

The Ti0 ₂ slurry (70.3 g, adjusted to pH 10 with NH ₄ OH) and the pre-composite (69.7 g, adjusted to pH 10 with NH ₄ OH), defoamer (0.25 g), and water (21.3 g) were combined and mixed with stirring substantially as carried out for Comparative Example 2. After about 10 min, the pH was adjusted to ~ 8.5 with citric acid. The mixture was then drawn down into a film and no grit was observed.

Kubelka-Munk S/mil Test Method

S/mil was determined for each of the final paint formulations as follows:

Two draw-downs were prepared on Black Release Charts (Leneta Form RC-BC) for each paint using a 1.5-mil Bird draw down bar and the charts allowed to dry overnight. Using a template, 3.25" x 4" rectangles were cut out with an X-ACTO knife on each chart. The y-reflectance was measured using a BYK Gardner 45 ^° Reflectomer in each of the scribed areas five times measuring on a diagonal starting at the top of the rectangle and the average y-reflectance recorded. A thick film draw down was prepared for each paint on Black Vinyl Charts (Leneta Form P 121-10N) using a 3" 25 mil block draw down bar and the charts were allowed to dry overnight. The y-reflectance was measured in five different areas of the draw down and the average y-reflectance recorded. Kubelka-Munk hiding value S is given by Equation 1 :

Equation 1

where X is the average film thickness, R is the average reflectance of the thick film and R _B is the average reflectance over black of the thin film. X can be calculated from the weight of the paint film (W _Pf ), the density (D) of the dry film; and the film area (A). Film area for a 3.25" x 4" template was 13 in ² .

X(mils) =

DQbs ! gal) x 1. %4(g / in ¹ ! lbs ! gal) x A(in )