Abstract:
A number of stable opacifying mixtures are disclosed which contain specific combinations and levels of titanium dioxide, thickeners, and dispersants. These stable mixtures may be employed in a method of making paints using prepaints or as a conventional component in a coating such as a paint, or in other end-uses where opacifying pigments are employed.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Applications Ser. No. 60/183,655 filed Feb. 18, 2000, Ser. No. 60/183,656 filed Feb. 18, 2000, and Ser. No. 60/247,639 filed Nov. 10, 2000. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention is related to stable mixtures containing opacifying pigments and more specifically, to stable mixtures containing select combinations and levels of titanium dioxide, a thickener, and a dispersant for use in making paint and other end products. 
     2. Description of Related Art 
     In co-pending U.S. provisional patent applications Ser. Nos. 60/183,655; 60/183,656; and 60/247,639; prepaints and a method of making paints from these prepaints is described. One of the prepaints is a mixture comprising at least one opacifying pigment, typically titanium dioxide. The other two prepaints may contain either an extender pigment or/and an emulsion polymeric binder. A key requirement for the prepaints is their compatibility with one another so that they may be mixed with each other in various ratios to make at least one paint line. Another key requirement is that the prepaints, whether comprising an opacifying pigment, an extender pigment, or an emulsion polymeric binder, be stable so that the prepaints may be prepared, shipped, and stored without failing, for example, failure by exhibiting non-homogeneity, syneresis, settling, gelling and/or viscosity changes. 
     With respect to prepaints containing an opacifying pigment, stability can be a serious problem. This is especially true when one considers that even the best commercially-available titanium dioxide slurries show some syneresis (&gt;2% by volume by visual inspection) upon storage and must be stirred vigorously and for a considerable length of time before use. 
     Hence, there is a need for stable mixtures containing specific combinations and levels of titanium dioxide, thickeners, and dispersants that may be employed, inter alia, as prepaints in a method of making paints or as conventional components in other end-uses where opacifying pigments are employed, including coatings, impregnants, inks, graphic arts, papers, textiles, caulks, mastics, adhesives, sealants, building products and leather. 
     SUMMARY OF THE INVENTION 
     Various fluid opacifying mixtures based on titanium dioxide are provided. Some of the mixture are stable and no mixing is required, others are stable with occasional mixing required, and others are stable with constant mixing required. 
     As used herein for all the mixtures “lbs/100 gallons” is based on the weight of the dry material, unless otherwise noted. 
     The following mixtures are stable and require no mixing when formulated as described below. 
     Mixture is a fluid opacifying pigment mixture comprising:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.2 to about 20 lbs/100 gallons of at least one hydrophobically-modified ethylene oxide-urethane polymer (HEUR) thickener selected from the group consisting of:
       (i) a HEUR having a C 4 -C 12  hydrophobe and a molecular weight of about 10,000 to about 200,000;   (ii) a HEUR having a C 6 -C 30  hydrophobe and a molecular weight of about 10,000 to about 200,000; and   (iii) combinations thereof; and   
       (c) about 1.5 to about 16 lbs/100 gallons of at least one dispersant selected from the group consisting of a maleic acid/diisobutylene copolymer, a butylmethacrylate/methacrylic acid copolymer, and an acrylic acid—hydroxypropyl acrylate copolymer;   

     Mixture 2 is a fluid opacifying pigment mixture comprising:
     (a) about 600 to about 1500 lbs/100 gallons of at least one interior-grade titanium dioxide;   (b) about 0.3 to about 5 lbs/100 gallons of at least one hydrophobically-modified, alkali-soluble or alkali-swellable emulsion (HASE) thickener having a C 6 -C 22  hydrophobe and a molecular weight of about 10,000 to about 7,000,000; and   (c) about 1.8 to about 23 lbs/100 gallons of at least one dispersant selected from the group consisting of maleic acid/diisobutylene copolymer, a butylmethacrylate/methacrylic acid copolymer, and an acrylic acid—hydroxypropyl acrylate copolymer;   

     Mixture 3 is a fluid opacifying pigment mixture comprising:
     (a) about 600 to about 1500 lbs/100 gallons of at least one interior-grade titanium dioxide;   (b) about 0.5 to about 3 lbs/100 gallons of at least one hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,000; and   (c) about 1.8 to about 23 lbs/100 gallons of at least one polyacrylic acid dispersant.   

     Mixture 4 is a fluid opacifying pigment mixture comprising:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 2 to about 6 lbs/100 gallons of at least one hydrophobically-modified hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,000; and   (c) about 1.8 to about 23 lbs/100 gallons of at least one polyacrylic acid dispersant.   

     Mixture 5 is a fluid opacifying pigment mixture containing:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.2 to about 10 lbs/100 gallons of at least one hydrophobically-modified hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,000;   (c) about 2 to about 10 lbs/100 gallons of at least one hydrophobically-modified ethylene oxide urethane polymer (HEUR) thickener having a C 4 -C 30  hydrophobe and a molecular weight of about 10,000 to about 200,000; and   (d) about 3.0 to about 22.5 lbs/100 gallons of at least one maleic acid/diisobutylene copolymer dispersant.   

     Mixture 6 is a fluid opacifying pigment mixture comprising:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.2 to about 10 lbs/100 gallons of at least one hydrophobically-modified hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,000;   (c) about 2 to about 10 lbs/100 gallons of at least one hydrophobically-modified ethylene oxide urethane polymer (HEUR) thickener having a C 4 -C 30  hydrophobe and a molecular weight of about 10,000 to about 200,000; and   (d) about 0.5 to about 22.5 lbs/100 gallons of at least one acrylic acid—hydroxypropyl acrylate dispersant.   

     The following mixtures are stable with occasional mixing required. 
     Mixture 7 is a fluid opacifying pigment mixture comprising:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 1 to about 10 lbs/100 gallons of at least one hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,0000 or hydrophobically-modified hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,000;   (c) optionally, about 2 to about 12 lbs/100 gallons of at least one hydrophobically-modified ethylene oxide urethane polymer (HEUR) thickener having a C 4 -C 30  hydrophobe and a molecular weight of about 10,000 to about 200,000 or at least one clay thickener; and   (d) about 0.5 to about 22.5 lbs/100 gallons of at least one acrylic acid/hydroxyl propyl acrylate dispersant.   

     Mixture 8 is a fluid opacifying pigment mixture containing:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.3 to about 5 lbs/100 gallons of at least one hydrophobically-modified, alkali-soluble or alkali-swellable emulsion (HASE) thickener having a C 6 -C 22  hydrophobe and a molecular weight of about 10,000 to about 7,000,000; and   (c) about 1.2 to about 45 lbs/100 gallons of at least one polyacrylic acid dispersant.   

     The following mixtures are stable with constant mixing required. They are formulated as described below. 
     Mixture 9 is a fluid opacifying pigment mixture containing:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.5 to about 10 lbs/100 gallons of at least one hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,0000 or about 0.5 to about 10 lbs/100 gallons of a hydrophobically-modified hydroxyalkyl cellulose thickener having a molecular weight of about 10,000 to about 10,000,000; and   (c) about 1.2 to about 18 lbs/100 gallons of at least one maleic acid/diisobutylene dispersant.   

     Mixture 10 is a fluid opacifying pigment mixture containing:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.1 to about 3 lbs/100 gallons of at least one hydrophobically-modified, alkali-soluble or alkali-swellable emulsion (HASE) thickener having a C 6 -C 22  hydrophobe and a molecular weight of about 10,000 to about 7,000,000; and   (c) about 0.6 to about 22.5 lbs/100 gallons of at least one acrylic acid/hydroxyl propyl acrylate dispersant.   

     Mixture 11 is a fluid opacifying pigment mixture containing:
     (a) about 600 to about 1500 lbs/100 gallons of at least one universal-grade titanium dioxide;   (b) about 0.1 to about 3 lbs/100 gallons of at least one hydrophobically-modified, alkali-soluble or alkali-swellable emulsion (HASE) thickener having a C 6 -C 22  hydrophobe and a molecular weight of about 10,000 to about 7,000,000; and   (c) about 0.6 to about 45 lbs/100 gallons of at least one maleic acid/diisobutylene dispersant.   

     Mixture 12 is a fluid opacifying pigment mixture containing:
     (a) about 600 to about 1500 lbs/100 gallons of at least one interior-grade titanium dioxide;   (b) about 0.2 to about 20 lbs/100 gallons of at least one hydrophobically-modified ethylene oxide urethane polymer (HEUR) thickener selected from the group consisting of:
       (i) a HEUR having a C 4 -C 12  hydrophobe and a molecular weight of about 10,000 to about 200,000;   (ii) a HEUR having a C 6 -C 30  hydrophobe and a molecular weight of about 10,000 to about 200,000; and   (iii) combinations thereof; and   
       (c) about 1.2 to about 8 lbs/100 gallons of at least one maleic acid/diisobutylene dispersant.   

     All of the above mixtures have a titanium dioxide (TiO 2 ) pigment volume concentration (PVC) of about 40 to 100%, a titanium dioxide (TiO 2 ) volume solids content of at least about 15%, and a Stormer viscosity of about 50 to about 250 KU. 
     All of the mixtures contain water and may contain optional additives selected from the group consisting of a defoamer, a surfactant, a coalescent, a base, a biocide, a mildeweide, a co-dispersant, a polymeric binder, a voided latex polymer and combinations thereof. 
     In order to prepare stable mixtures of opacifying pigments, one must follow strict rules in selecting the types and level of specific ingredients, using the general approach set out below:
         select the type and level of titanium dioxide based on whether the final paint will be for exterior or interior use with a universal-grade being selected for interior, exterior, or interior/exterior use and with an interior-grade being selected for interior use only;   select the appropriate rheology modifier/thickener based on the type of titanium dioxide selected;   select the appropriate dispersant based on the type of rheology modifier/thickener selected;   determine the level of dispersant necessary to produce a stable final mixture; and   determine the level of rheology modifier/thickener required to produce a stable final mixture.       

     As used herein, the term “stable” applies to those mixtures that meet all of the following criteria, as set out in the Stability Tests described below, after being stored at a temperature of at least 120° C. for at least ten (10) days:
         (1) there is less than 2% by volume of syneresis in the mixture (determined by inspecting the pigment mixture visually) (referred to herein as “Stability Test 1”).   (2) the mixture has a Brookfield viscosity (measured at a shear rate of 1.25 sec −1 ) of less than 100,000 centipoise, preferably less than 50,000 centipoise after cooling to ambient temperature (22-25° C.), but prior to mechanical shearing (referred to herein as “Stability Test 2”).   (3) the ratio of the Brookfield viscosity (measured at a shear rate of 1.25 sec −1 ) after heat aging to the Brookfield viscosity (measured at a shear rate of 1.25 sec −1 ) prior to heat aging is no greater than 3 after the mixture is cooled to ambient temperature (22-25° C.) and after mechanical shearing using a propeller-type mixer (referred to herein as “Stability Test 3”). Commercial titanium dioxide slurries do not pass Stability Test 1 and must be stirred, sometimes constantly, prior to use. Mixtures having Brookfield viscosities higher than those specified in Stability Test 2 tend to gell and resist flow and therefore are difficult to pump in conventional equipment. Stability Test 3 is used to determine whether or not the mixture developed, or will develop, a gel network resistant to shear thinning (mixing) during storage.       

     The mixing conditions used to categorize the stability of the fluid opacifying pigment mixtures are as follows:
     (1) mixtures which require no mixing or other form of agitation over typical storage times (at least 30 days) and under storage conditions where the temperature can be as high as 140° F. and as low as 25° F. to remain stable are referred to herein as “stable with no mixing required”)(require mixing over 0% of storage time);   (2) mixtures which require periodic or occasional mixing or other forms of agitation to re-homogenize or break any minimal or slight structure formed over the typical storage times and conditions described above are referred to herein as “stable with occasional mixing required”)(require mixing over &gt;0% of storage time); and   (3) mixtures which require constant mixing or other forms of agitation to re-homogenize or break any significant structure formed over the typical storage times and conditions described above (are referred to herein as “stable with constant mixing required”)(require mixing over &gt;50% of storage time).
 
It should be noted that while the “stable with no mixing required” condition requires no mixing or other form of agitation to remain stable, applying some form of mixing or agitation to the mixture (whether occasional or constant) does not exclude that particular mixture from the definition of a stable mixture with “no mixing required”. Likewise, it should be noted that while the “stable with occasional mixing required” condition requires only occasional mixing or other form of agitation to remain stable, applying constant mixing or agitation to the mixture does not exclude that particular mixture from the definition of a stable mixture with “occasional mixing required”.
   

     Any type of mixer or agitator may be used such as, but not limited to an impellar, a recirculator, a shaker, a mill, a rotator, a bubbler, a sonicator, a pump or a like means suitable to move the mixture about itself. 
     The mixtures herein may be employed as prepaints in systems using delayed product differentiation as described in U.S. patent applications Ser. No. 60/183,655 filed Feb. 18, 2000; Ser. No. 60/183,656 filed Feb. 18, 2000; Ser. No. 60/247,639 filed Nov. 10, 2000], as well as employed as replacements for conventional mixtures containing opacifying pigments, such as titanium dioxide slurries, mill bases, colorant dispersions, coating colors, and the like. 
     The pigment volume concentration (PVC) is a measure of how “binder-rich” a formulation is. It is calculated using the formula: 
         PVC   ⁡     (   %   )       =         (       volume   ⁢           ⁢   of   ⁢           ⁢     pigment   ⁡     (   s   )         +     volume   ⁢           ⁢     extender   ⁡     (   s   )           )       (       volume   ⁢           ⁢   of   ⁢           ⁢     pigment   ⁡     (   s   )         +     volume   ⁢           ⁢     extender   ⁡     (   s   )         +     volume   ⁢           ⁢     binder   ⁡     (   s   )               ×   100         
 
     The volume solids content (VS) is the dry volume of pigment(s) plus the dry volume of extender(s) plus the dry volume of binder(s). It is calculated using the formula: 
         VS   ⁡     (   %   )       =                 dry   ⁢           ⁢   volume   ⁢           ⁢   of   ⁢           ⁢     pigment   ⁡     (   s   )         +                 dry   ⁢           ⁢   volume   ⁢           ⁢   of   ⁢           ⁢     extender   ⁡     (   s   )         +     dry   ⁢           ⁢   volume   ⁢           ⁢   of   ⁢           ⁢     binder   ⁡     (   s   )                   total   ⁢           ⁢   volume   ⁢           ⁢   of   ⁢           ⁢   formulation       ×   100.         
 
     If additives are present, their volumes are not included in determining the total dry volume. 
     The titanium dioxide pigment volume concentration (TiO 2  PVC) is a measure of how “binder-rich” a formulation is relative to only the titanium dioxide (TiO 2 ) content. It is calculated using the formula: 
           TiO   2     ⁢     PVC   ⁡     (   %   )         =         volume   ⁢           ⁢   of   ⁢           ⁢     TiO   2     ⁢             ⁢             ⁢     pigment   ⁡     (   s   )           (       volume   ⁢           ⁢   of   ⁢           ⁢     pigment   ⁡     (   s   )         +     volume   ⁢           ⁢     extender   ⁡     (   s   )         +     volume   ⁢           ⁢     binder   ⁡     (   s   )               ×   100         
 
     The titanium dioxide volume solids content (TiO 2  VS) is the dry volume of TiO 2  pigment(s) plus the dry volume of extender(s). It is calculated using the formula: 
           TiO   2     ⁢     VS   ⁡     (   %   )         =         dry   ⁢           ⁢   volume   ⁢           ⁢   of   ⁢           ⁢     TiO   2     ⁢           ⁢     pigment   ⁡     (   s   )           total   ⁢           ⁢   volume   ⁢           ⁢   of   ⁢           ⁢   formulation       ×   100.         
 
If additives are present, their volume is not included in determining the total dry volume.
 
Opacifying Pigments
 
     Suitable opacifying pigments include:
     (1) white pigments which impart white scattering power to a paint across all visible wave lengths without a high degree of absorption; and   (2) auxiliary hiding pigments including inorganic and organic solids or voided latex polymers which do not impart a primary color or hiding power to a paint although they may have secondary influences on those properties.   

     Such opacifying pigments include titanium dioxide or a combination of titanium dioxide and auxiliary hiding pigments such as voided latex polymer particles, zinc oxide, lead oxide, a synthetic polymer pigment, and mixtures thereof. Rutile and anatase grades of titanium dioxide are suitable for use herein. Rutile titanium dioxide is preferred. The surface of the titanium dioxide may be treated with various organic or inorganic surface treatments, e.g., the oxides of silica, alumina, and zirconia. Fumed titanium oxide is also useful herein. 
     For specific mixtures, certain grades of titanium dioxide are required. For example, for some of the mixtures universal-grade titanium dioxide may be used, whereas for others interior-grade titanium dioxide must be used. As used herein, “universal-grade” titanium dioxide means titanium dioxide that is suitable for use in both interior and exterior applications and which is typically treated with oxides of alumina (about 1 to about 7%), silica (up to about 15%) and zirconia (up to about 15%). As used herein, “interior-grade” titanium dioxide means titanium dioxide that is only suitable for use in interior applications which is typically treated with only the oxides of alumina (about 1 to about 7%) or a combinations of the oxides of alumina (about 1 to about 7%) with the oxides of silica (up to about 5%). This grade of titanium dioxide is likely to provide poorer water resistance in final coatings than the universal-grade titanium dioxide). 
     The voided latex particles useful herein have a particle size diameter of about 100 nm to about 2,500 nm and a void fraction of about 10% to about 75%. Preferably, the particles have a particle size of about 500 run to about 1,100 nm. The particles must have at least one void, but they may have multiple voids, non-spherical voids, interconnected voids, voids having channels connected to the outside of the particles, and they can encompass structures described as vesiculated and sponge-like. Preferably, the particles have a single void. They have a glass transition temperature (Tg), as measured by differential scanning calorimetry at a rate of 20° C./minute, of at least about 20° C., preferably at least about 50° C. The higher the Tg, the harder the particle is and the less likely it is to collapse. If the particles collapse, they are unable to contribute to hiding. The voided latex particles may be prepared by conventional polymerization processes known in the art, such as those disclosed in U.S. Pat. Nos. 3,784,391, 4,427,836; 4,469,825; 4,594,363; 4,798,691; 4,880,842; 4,908,271; 4,972,000; 5,041,464, 5,157,084; 5,216,044, 5,494,971; 5,545,695; and 6,020,435, as well as Japanese Patent Applications 60/223,873, 61/62510, 61/66710, 61/86941, 62/127336, 62/156387, 01/185311, and 02/140272. 
     Thickener 
     Suitable thickeners include both non-associative, water-soluble/water-swellable thickeners and associative thickeners. Suitable non-associative, water-soluble/water-swellable thickeners include polyvinyl alcohol (PVA), alkali soluble or alkali swellable emulsions known in the art as ASE emulsions, and cellulosic thickeners such as hydroxyalkyl celluloses including hydroxymethyl cellulose, hydroxyethyl cellulose and 2-hydroxypropyl cellulose, sodium carboxymethyl cellulose (SCMC), sodium carboxymethyl cellulose, 2-hydroxyethyl cellulose, 2-hydroxypropyl methyl cellulose, 2-hydroxyethyl methyl cellulose, 2-hydroxybutyl methyl cellulose, 2-hydroxyethyl ethyl cellulose, and the like. Suitable associative thickeners include hydrophobically-modified, alkali-soluble emulsions known in the art as HASE emulsions, hydrophobically-modified ethylene oxide-urethane polymers known in the art as HEUR thickeners, hydrophobically-modified cellulosics such as hydrophobically-modified hydroxyethyl cellulose, hydrophobically-modified polyacrylamides, and the like. Also useful as thickeners are fumed silica, attapulgite clay and other types of clay, titanate chelating agents, and the like. 
     Suitable dispersants include anionic polymers such as homopolymers and copolymers based on polycarboxylic acids, including those that have been hydrophobically- or hydrophilically-modified, e.g., polyacrylic acid, polymethacrylic acid, maleic anhydride and copolymers thereof with each other and with various monomers such as styrene, acrylate or methacrylate, diisobutylene, and other hydrophilic or hydrophobic comonomers. Suitable dispersants further include salts of the above dispersants and mixtures thereof. 
     The opacifying mixtures may include certain optional additives including defoamers, surfactants, coalescents, biocides, mildewcides, co-dispersants, dispersing resins, latex adsorbing resins, polymeric binders, and the voided latex polymers (described above). 
     Suitable defoamers include silicone-based and mineral oil-based defoamers and the like. 
     Suitable surfactants include cationic, anionic and non-ionic surfactants. 
     Suitable coalescents, plasticizers, and other optional solvents include ethylene glycol, propylene glycol, hexylene glycol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TEXANOL™), glycol ethers, mineral spirits, methyl carbitol, butyl carbitol, phthalates, adipates, and the like. 
     Suitable mildewcides and biocides include zinc oxide, isothiazolones, triazoles, and the like. 
     Suitable co-dispersants include non-ionic, anionic, and cationic dispersants such as 2-amino 2-methyl 1-propanol, dimethyl amino ethanol, potassium tripolyphosphate, trisodium polyphosphate, citric acid and other carboxylic acids, and the like. 
     Latex polymer binders are polymers or prepolymers which form the primary film of a paint. They bind the pigment and/or extenders, provide the required paint flow, and determine the gloss and hardness of the final paint film. The binder selected will depend upon the final use of the formulated paints. Binders suitable for exterior paints are generally suitable for interior paints, but binders suitable for interior paints may not be suitable for exterior paints. Suitable binders include, but are not limited to, homopolymers, copolymers, or terpolymers such as, for example, polyvinyl acetate, styrene-acrylic, styrene-butadiene, vinyl acetate-acrylic, ethylene-vinyl acetate, vinyl acetate-vinyl versatate, vinyl acetate-vinyl maleate, vinyl acetate-vinyl chloride-acrylic, ethylene-vinyl acetate-acrylic, and urethane polymers, optionally containing up to 10% by weight of functional groups (for example, but not limited to, carboxylic acid, phosphate, sulfate, sulfonate, amide and combinations thereof), other non-functional monomers, and mixtures thereof. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     All ranges disclosed herein are inclusive and the minimums and maximums of the nested ranges are combinable. All levels are in dry pounds/100 gallons i.e., pounds of solids/100 gallons of the mixtures unless otherwise noted. After the required ingredients and optional ingredients are combined, sufficient water is added to give a total of 100 gallons of the mixture. 
     The following optional ingredients may be included in any of the combination ranges shown below: 
                                                   Optional Ingredients                    Preferred       Preferred       Ingredient   Types   Types   Level   Level               Defoamer   any   solvent-   1-5   2-3               based,               silicone-               based       Surfactant   nonionic,   nonionic,   1-7   1-5           anionic, cationic   anionic       Solvent and   propylene glycol,   propylene    1-200    1-100       coalescent   ethylene glycol,   glycol,           hexylene glycol,   Texanol ®           2,2,4-trimethyl-1-3-           pentanediol           monoisobutyrate           (Texanol ®),           butyl carbitol,           methyl carbitol,           mineral spirits,       Base   ammonium   ammonium   up to 10   up to 5            hydroxide,   hydroxide,           sodium hydroxide,   AMP-95           potassium           hydroxide,           2-amino 2-methyl           1-propanol (AMP)       Biocide   isothiazolones,   iso-   up to 5    up to 3            carbamates,   thiazolones           thiazoles,           phthalonitriles,           dioxanes,           hydantoins,           carbanilides,           triazines, ureas,           thiocyanates       Mildewcide   isothiazolones,   iso-   up to 20   up to 10           carbamates,   thiazolones           thiazoles,           phthalonitriles,           dioxanes,           hydantoins,           carbanilides,           triazines, ureas,           thiocyanates       Co-   2-amino 2-methyl   citric acid,   up to 5    up to 2        dispersant   1-propanol   KTTP, AMP           (AMP-95), dimethyl           amino ethanol           (DMEA), potassium           tripolyphosphate           (KTTP), trisodium           polyphosphate           (TSPP),       Polymeric   See above   vinyl acrylic,    up to 150   up to 80       Binder   description   vinyl acetate,               styrene               acrylic       Voided latex   See above   x    up to 100   up to 60       polymer   description                    
Combination No. 1
 
     The combinations shown below do not require mixing to remain stable. They are exemplified in Example 1. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   MA/DIB,   MA/DIB   1.5-16    3.7-14        persant   BMA/MAA,           AA/HPA, SMA       Thick-   HEUR effective   HEUR   0.2-20    10-16       ener   hydrophobe   effective           C 4 -C 12  MW   hydrophobe           10,000-200,000,   C 4 -C 12  and               MW 12,000-               150,000           HEUR effective   HEUR   0.8-5     0.2-2             hydrophobe   effective           C 6 -C 30  MW   hydrophobe           10,000-200,000,   C 6 -C 24  and           or combinations   MW 12,000-           thereof   150,000       TiO 2     Universal grade   Universal TiO 2      600-1500    700-1400           coated with   coated with           1%-7% Al 2 O 3 ,   1.5-5% Al 2 O 3             up to 15% SiO 2     1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 2
 
     The following combinations do not require mixing to remain stable. They are exemplified in Example 2. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   MA/DIB,   PAA   1.8-23     3.5-16.8       persant   BMA/MAA,           AA/HPA, PAA       Thick-   HASE effective   HASE effective   0.3-5     1-3       ener   hydrophobe   hydrophobe           C 6 -C 22  MW   C 6 -C 18  and           10,000-7,000,000   MW 100,000-               5,000,000       TiO 2     Interior grade   Interior grade    600-1500    700-1400           coated with   coated with           1-7% Al 2 O 3 /   2-5% Al 2 O 3 /           0-5% SiO 2  0-5%   0-3% SiO 2                      
Combination No. 3
 
     The following combinations do not require mixing to remain stable. They are exemplified in Example 3. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   PAA   PAA   1.8-23     3.5-16.8       persant       Thick-   Hydroxy-   Hydroxyethyl   0.5-3     1-2       ener   alkylcellulose and   cellulose           combinations   MW 100,000-           thereof MW   2,000,000           10,000-           10,000,000       TiO 2     Interior grade   Interior grade    600-1500    700-1400           coated with   coated with           1-7% Al 2 O 3     2-5% Al 2 O 3 /           up to 5% SiO 2     up to 3% SiO 2                      
Combination No. 4
 
     The following combinations do not require mixing to remain stable. They are exemplified in Example 4. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   PAA   PAA   1.8-23     3.5-16.8       persant       Thick-   Hydrophobically-   Hydro-   2-6   3-5       ener   modified   phobically-           hydroxy-   modified           alkyllcellulose   hydroxy-           MW 10,000-   ethylcellulose           10,000,000   MW 50,000-               2,000,000       TiO 2     Universal coated   Universal    600-1500    700-1400           with 1-7%   coated with           Al 2 O 3 ,   1.5-5% Al 2 O 3 ,           up to 15% SiO 2 ,   1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 5
 
     The following combinations do not require mixing to remain stable. They are exemplified in Example 5. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   MA/DIB or   MA/DIB or    3.0-22.5    5.6-16.8       persant   AA/HPA   AA/HPA   MA/DIB   MA/DIB                    0.5-22.5   2.8-14                    AA/HPA   AA/HPA       Thick-   Hydrophobically-   Hydro-   0.2-10    0.5-5         ener   modified   phobically-           hydroxyalkyl   modified           cellulose   hydroxyethyl           MW 10,000-   cellulose           10,000,000   MW 50,000-               2,000,000       Thick-   HEUR effective   HEUR    2-10    5-10       ener   hydrophobe   effective           C 4 -C 30     hydrophobe           MW 10,000-   C 6 -C 24             200,000   MW 12,000-               150,000       TiO 2     Universal coated   Universal    600-1500    700-1400           with 1-7%   coated with           Al 2 O 3 ,   1.5-5% Al 2 O 3 ,           up to 15% SiO 2 ,   1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 6
 
     The following combinations requires occasional mixing to remain stable. They are exemplified in Example 6. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   AA/HPA   AA/HPA   0.5-22.5   2.8-14         persant       Thick-   Hydrophobically-   Hydro-   1-10   2-7        ener   modified   phobically-           hydroxyalkyl   modified           cellulose   hydroxyethyl           MW 10,000-   cellulose           1,000,000   MW 50,000-           or   1,000,000           Hydroxyethyl   Hydroxyethyl   1-10   2-7            cellulose   cellulose           MW 10,000-   MW 100,000-           1,000,000   1,000,000           or           combinations of           the above           or           combinations of       2-12   4-10           the above           with:           HEUR effective   HEUR   2-12   3-6            hydrophobe   effective           C 4 -C 30     hydrophobe           MW 10,000-   C 6 -C 24             200,000   MW 12,000-           or   150,000           attapulgite clay       TiO 2     Universal coated   Universal   600-1500   700-1400           with 1.0-7%   coated with           Al 2 O 3 ,   1.5-5% Al 2 O 3 ,           up to 15% SiO 2 ,   1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 7
 
     The following combinations requires occasional mixing to remain stable. They are exemplified in Example 7. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   PAA   PAA   1.2-45    3.5-28        persant       Thick-   HASE effective   HASE effective   0.3-5     1.0-3         ener   hydrophobe   hydrophobe           C 6 -C 22     C 6 -C 18             MW 10,000-   MW 100,000-           7,000,000   5,000,000       TiO 2     Universal coated   Universal    600-1500    700-1400           with 1-7%   coated with           Al 2 O 3 ,   1.5-5% Al 2 O 3 ,           up to 15% SiO 2 ,   1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 8
 
     The following combinations requires constant mixing to remain stable. They are exemplified in Example 8. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   MA-DIB   MA-DIB   1.2-18    3.5-14        persant       Thick-   Hydrophobically-   Hydro-   0.5-10    0.5-8         ener   modified   phobically-           hydroxyalkyl   modified           cellulose   hydroxyethyl           MW 10,000-   cellulose           1,000,000   MW 50,000-           or   1,000,000           Hydroxyethyl   Hydroxyethyl           cellulose   cellulose           MW 10,000-   MW 100,000-           1,000,000   1,000,000           or           combinations of           the above       TiO 2     Universal coated   Universal    600-1500    700-1400           with 1-7%   coated with           Al 2 O 3 ,   1.5-5% Al 2 O 3 ,           up to 15% SiO 2 ,   1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 9
 
     The following combinations requires constant mixing to remain stable. 
                                             Ingre-       Preferred       Preferred       dients   Types   Types   Level   Level                   Dis-   AA/HPA   AA/HPA    0.6-22.5   2.8-14        persant       Thick-   HASE effective   HASE effective   0.1-3     0.3-2         ener   hydrophobe   hydrophobe           C 6 -C 22     C 6 -C 18             MW 10,000-   MW 100,000-           7,000,000   5,000,000       TiO 2     Universal coated   Universal    600-1500    700-1400           with 1-7%   coated with           Al 2 O 3 ,   1.5-5% Al 2 O 3 ,           up to 15% SiO 2 ,   1.2-12% SiO 2 ,           up to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 10
 
     The following combinations will require constant mixing to remain stable. 
                                             Ingred-       Preferred       Preferred       ients   Types   Types   Level   Level                   Dispersant   MA/DIB   MA/DIB   0.6-45    2.8-21        Thickener   HASE effective   HASE effective   0.1-3     0.3-2             hydrophobe   hydrophobe           C 6 -C 22  MW   C 6 -C 18  MW           10,000-   100,000-           7,000,000   5,000,000       TiO 2     Universal coat-   Universal coat-    600-1500    700-1400           ed with 1-7%   ed with 1.5-5%           Al 2 O 3 , up to   Al 2 O 3 ,           15% SiO 2 , up   1.2-12% SiO 2 ,           to 15% ZrO 2     up to 4% ZrO 2                      
Combination No. 11
 
     The following combinations require constant mixing to remain stable. 
     
       
         
               
               
               
               
               
             
           
               
                   
               
               
                 Ingred- 
                   
                 Preferred 
                   
                 Preferred 
               
               
                 ients 
                 Types 
                 Types 
                 Level 
                 Level 
               
               
                   
               
             
             
               
                 Dispersant 
                 MA/DIB 
                 MA/DIB 
                 1.2-18  
                 3.5-14  
               
               
                 Thickener 
                 HEUR effec- 
                 HEUR effec- 
                 0.2-20  
                 10-16 
               
               
                   
                 tive hydro- 
                 tive hydro- 
               
               
                   
                 phobe C 4 -C 12   
                 phobe C 4 -C 12   
               
               
                   
                 MW 10,000- 
                 MW 12,000- 
               
               
                   
                 200,000 or 
                 150,000 
               
               
                   
                 HEUR effec- 
                 HEUR effec- 
                 0.8-5   
                 0.2-2   
               
               
                   
                 tive hydro- 
                 tive hydro- 
               
               
                   
                 phobe C 6 -C 30    
                 phobe C 6 -C 24   
               
               
                   
                 average MW 
                 MW 12,000- 
               
               
                   
                 10,000- 
                 150,000 
               
               
                   
                 200,000 or 
               
               
                   
                 combinations 
               
               
                   
                 thereof 
               
               
                 TiO 2   
                 Interior grade 
                 Interior grade 
                  600-1500 
                  700-1400 
               
               
                   
                 coated with 
                 coated with 
               
               
                   
                 1-7% Al 2 O 3 , 
                 2-5% Al 2 O 3 , 
               
               
                   
                 up to 5% SiO 2   
                 up to 3% SiO 2   
               
               
                   
               
             
          
         
       
     
     Test Procedures 
     The Stormer viscosity of the mixtures is measured using ASTM method D562. 
     The Brookfield viscosity of the mixtures is measured using spindle #4 of a Brookfield viscometer at 6 rpm. 
     The ICI viscosity of the mixtures is measured using ASTM method D3205-77. 
     In the following examples, the mixtures may be prepared using a laboratory mixer having a 45° pitch stirring blade. The water and optional dispersant, defoamer, surfactant and/or biocide are combined and mixed. The titanium dioxide slurry is slowly added and the mixture is stirred for 15-20 minutes. The binder and optional coalescent, rheology modifier, ammonia, and additional water, if necessary, are then added. 
     In the above description and in the examples, the following abbreviations are used: 
     
       
         
               
             
               
               
             
           
               
                   
               
               
                 Abbreviations 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 AA 
                 Acrylic acid 
               
               
                 PAA 
                 Polyacrylic acid 
               
               
                 MA/DIB 
                 Maleic acid/diisobutylene copolymer 
               
               
                 AA/HPA 
                 Acrylic acid/hydroxypropyl acid 
               
               
                 BMA/MAA 
                 Butylmethacrylate/methacrylic acid copolymer 
               
               
                 SMA 
                 Styrene or alpha methylstyrene/alkylacrylate (optional)/ 
               
               
                   
                 methacrylic or acrylic acid copolymers or terpolymers 
               
               
                 HEC 
                 Hydroxyethyl cellulose 
               
               
                 HMHEC 
                 Hydrophobically-modified HEC 
               
               
                 HEUR 
                 Hydrophobically-modified ethylene oxide-based urethane 
               
               
                   
                 block copolymers 
               
               
                 HASE 
                 Hydrophically-modified alkali soluble emulsions 
               
               
                 TiO 2   
                 Titanium dioxide 
               
               
                 Al 2 O 3   
                 Alumina or oxide of aluminum 
               
               
                 SiO 2   
                 Silica or oxide of silicon 
               
               
                 ZrO 2   
                 Zirconium dioxide 
               
               
                 cps 
                 centipoises 
               
               
                 MW 
                 molecular weight as measured by gel permeation 
               
               
                   
                 chromatography 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 
     Example 1 
     Mixtures A to E described below will require no mixing to remain stable. 
     
       
         
               
               
               
             
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                   
                 A 
               
               
                   
                 Ingredients 
                 lbs/100 gallons 
               
               
                   
                   
               
             
          
           
               
                   
                 Grind prepared on 
                   
               
               
                   
                 Cowles disperser 
               
               
                   
                 Water 
                 258.35 
               
               
                   
                 Propylene glycol 
                 50 
               
               
                   
                 Tamol ™ 731 MA/DIB 
                 53.42 
               
               
                   
                 dispersant 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Triton CF-10 surfactant 
                 2.00 
               
               
                   
                 Kathon ® LX 1.5% 
                 2.00 
               
               
                   
                 biocide 
               
               
                   
                 Ti-Pure ® R706 universal- 
                 1335.56 
               
               
                   
                 grade TiO 2   
               
               
                   
                 Letdown prepared on 
               
               
                   
                 Cowles disperser 
               
               
                   
                 Ammonia hydroxide 
                 0.6 
               
               
                   
                 (28%) 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Acrysol ® RM-2020NPR 
                 30.00 
               
               
                   
                 HEUR thickener 
               
               
                   
                 Letdown (on low speed 
               
               
                   
                 mixer) 
               
               
                   
                 Acrysol ® RM-2020NPR 
                 40.40 
               
               
                   
                 HEUR thickener 
               
               
                   
                 Water 
                 68.96 
               
               
                   
                 KU initially after 
                 90 
               
               
                   
                 preparation 
               
               
                   
                 pH initially after 
                 9.20 
               
               
                   
                 preparation 
               
               
                   
                 ICI initially after 
                 2.8 
               
               
                   
                 preparation 
               
               
                   
                 Brookfield viscosity 
                 2500 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale prepared 
                 50 
               
               
                   
                 (gallons) 
               
               
                   
                   
               
             
          
           
               
                   
                 B 
                 C 
                 D 
                 E 
               
               
                   
                 lbs/100 
                 lbs/100 
                 lbs/100 
                 lbs/100 
               
               
                 Ingredients 
                 gallons 
                 gallons 
                 gallons 
                 gallons 
               
               
                   
               
             
          
           
               
                 Grind prepared on 
                   
                   
                   
                   
               
               
                 Cowles disperser 
               
               
                 Water 
                 130 
                 130 
                 130 
                 130 
               
               
                 Propylene glycol 
                 50 
                 50 
                 50 
                 50 
               
               
                 Tamol ® 731 MA/DIB 
                 29.38 
                 29.38 
                 29.38 
                 29.38 
               
               
                 dispersant 
               
               
                 Foamaster ® VL 
                 3.00 
                 3.00 
                 3.00 
                 3.00 
               
               
                 defoamer 
               
               
                 Triton CF-10 surfactant 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
               
               
                 Kathon ® LX 1.5% 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
               
               
                 biocide 
               
               
                 Ti-Pure ® R-706 
                 734.56 
                 734.56 
                 734.56 
                 734.56 
               
               
                 universal-grade TiO 2   
               
               
                 Rhoplex ® SG-10M 
                 151.20 
                 151.20 
                 151.20 
                 151.20 
               
               
                 acrylic binder 
               
               
                 Texanol ®  coalescent 
                 12.5 
                 12.5 
                 12.5 
                 12.5 
               
               
                 Ammonium hydroxide 
                 0.60 
                 0.60 
                 0.60 
                 0.60 
               
               
                 (28%) 
               
               
                 Ropaque ® Ultra opaque 
                 164.44 
                 164.44 
                 164.44 
                 164.44 
               
               
                 polymer 
               
               
                 Acrysol ® RM- 
                 30 
                 30 
                 30 
                 30 
               
               
                 2020NPR HEUR 
               
               
                 thickener 
               
               
                 Letdown prepared on low 
               
               
                 speed mixer) 
               
               
                 Co-thickener type 
                 Acrysol ® 
                 Acrysol ® 
                 Acrysol ® 
                 Acrysol ® 
               
               
                   
                 RM- 
                 RM-825 
                 SCT-275 
                 RM-12W 
               
               
                   
                 2020NPR 
                 HEUR 
                 HEUR 
                 HEUR 
               
               
                   
                 HEUR 
               
               
                 Level of co-thickener 
                 33.5 
                 2.24 
                 2.63 
                 4.84 
               
               
                 water 
                 60.0 
                 91.2 
                 90.8 
                 88.5 
               
               
                 KU initially after 
                 93 
                 99 
                 96 
                 96 
               
               
                 preparation 
               
               
                 pH initially after 
                 8.80 
                 8.78 
                 8.76 
                 8.74 
               
               
                 preparation 
               
               
                 ICI initially after 
                 3.0 
                 1.7 
                 1.8 
                 1 7 
               
               
                 preparation 
               
               
                 Brookfield viscosity 
                 3010 
                 3710 
                 6010 
                 24000 
               
               
                 (cps at 1.25 sec −1 ) 
               
               
                 Actual scale prepared 
                 50 
                 50 
                 50 
                 50 
               
               
                 (gallons) 
               
               
                   
               
             
          
         
       
     
     Example 2 
     Mixtures A to G described below will require no mixing to remain stable. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
             
             
               
                   
                 A 
                 B 
                 C 
                 D 
               
               
                   
                 lbs/100 
                 lbs/100 
                 lbs/100 
                 lbs/100 
               
               
                 Ingredients 
                 gallons 
                 gallons 
                 gallons 
                 gallons 
               
               
                   
               
             
          
           
               
                 Grind prepared on 
                   
                   
                   
                   
               
               
                 Cowles disperser 
               
               
                 Water 
                 228.00 
                 228.00 
                 228.00 
                 228.00 
               
               
                 Propylene glycol 
                 50.00 
                 50.00 
                 50.00 
                 50.00 
               
               
                 Tamol ® 1254 
                 38.16 
                 38.16 
                 38.16 
                 38 16 
               
               
                 AA/MAA dispersant 
               
               
                 Triton ® CF-10 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
               
               
                 surfactant 
               
               
                 Foamaster ® VL 
                 1.50 
                 1.50 
                 1.50 
                 1.50 
               
               
                 defoamer 
               
               
                 Kathon ® LX 1.5% 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
               
               
                 biocide 
               
               
                 Ti-Pure ® R900 interior- 
                 1335.52 
                 1335.52 
                 1335.52 
                 1335.52 
               
               
                 grade TiO 2   
               
               
                 Letdown prepared on 
               
               
                 Cowles disperser 
               
               
                 Foamaster ® VL 
                 1.50 
                 1.50 
                 1.50 
                 1.50 
               
               
                 defoamer 
               
               
                 Water 
                 97.00 
                 97.00 
                 97.00 
                 97.00 
               
               
                 Ammonium hydroxide 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
               
               
                 (28%) 
               
               
                 Acrysol ® DR-1 HASE 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
               
               
                 thickener 
               
               
                 Letdown prepared on low 
               
               
                 speed mixer 
               
               
                 Acrysol ® DR-1 HASE 
                 4.0 
                 5.0 
                 6.0 
                 7.0 
               
               
                 thickener 
               
               
                 Water 
                 83.96 
                 82.96 
                 81.96 
                 80.96 
               
               
                 KU initially after 
                 77 
                 80 
                 83 
                 87 
               
               
                 preparation 
               
               
                 pH initially after 
                 0.4 
                 0.5 
                 0.6 
                 0.6 
               
               
                 preparation 
               
               
                 ICI initially after 
                 9.06 
                 8.98 
                 8.89 
                 8.79 
               
               
                 preparation 
               
               
                 Brookfield viscosity 
                 12800 
                 14500 
                 15000 
                 16700 
               
               
                 (cps at 1.25 sec −1 ) 
               
               
                 Actual scale prepared 
                 50 
                 50 
                 50 
                 50 
               
               
                 (gallons) 
               
               
                   
               
             
          
           
               
                   
                 E 
                 F 
                 G 
               
               
                   
                 lbs/100 gallons 
                 lbs/100 gallons 
                 lbs/100 gallons 
               
               
                   
                   
               
             
          
           
               
                 Grind prepared on 
                   
                   
                   
               
               
                 Cowles disperser 
               
               
                 Water 
                 228.00 
                 228.00 
                 228.00 
               
               
                 Propylene glycol 
                 50.00 
                 50.00 
                 50.00 
               
               
                 Tamol ® 1254 
                 38.16 
                 38.16 
                 38.16 
               
               
                 AA/MAA dispersant 
               
               
                 Triton ® CF-10 
                 2.00 
                 2.00 
                 2.00 
               
               
                 surfactant 
               
               
                 Foamaster ® VL 
                 1.50 
                 1.50 
                 1.50 
               
               
                 defoamer 
               
               
                 Kathon ® LX 1.5% 
                 2.00 
                 2.00 
                 2.00 
               
               
                 biocide 
               
               
                 Ti-Pure ® R900 in- 
                 1335.52 
                 1335.52 
                 1335.52 
               
               
                 terior grade TiO 2   
               
               
                 Letdown prepared on 
               
               
                 Cowles disperser 
               
               
                 Foamaster ® VL 
                 1.50 
                 1.50 
                 1.50 
               
               
                 defoamer 
               
               
                 Water 
                 97.00 
                 97.00 
                 97.00 
               
               
                 Letdown prepared on 
               
               
                 low speed mixer 
               
               
                 Thickener type 
                 Acrysol ® DR- 
                 Acrysol ® DR- 
                 Acrysol ® DR- 
               
               
                   
                 73 HASE 
                 1 HASE 
                 3 HASE 
               
               
                 Level of thickener 
                 6.86 
                 6.08 
                 6.04 
               
               
                 Ammonia hydroxide 
                 0.40 
                 0.30 
                 0.22 
               
               
                 (28%) 
               
               
                 Water 
                 82.08 
                 82.96 
                 83.08 
               
               
                 KU initially after 
                 81 
                 81 
                 81 
               
               
                 preparation 
               
               
                 pH initially after 
                 0.8 
                 0.6 
                 0.7 
               
               
                 preparation 
               
               
                 ICI initially after 
                 9.01 
                 8.96 
                 8.99 
               
               
                 preparation 
               
               
                 Brookfield viscosity 
                 15700 
                 15300 
                 15200 
               
               
                 (cps at 1.25 sec −1 ) 
               
               
                 Actual scale prepared 
                 50 
                 50 
                 50 
               
               
                 (gallons) 
               
               
                   
               
             
          
         
       
     
     Example 3 
     Mixture A described below will require no mixing to remain stable. 
     
       
         
               
               
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 A 
               
               
                   
                 Ingredients 
                 lbs/100 gallons 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Grind prepared on Cowles disperser 
                   
               
               
                   
                 Water 
                 228.00 
               
               
                   
                 Propylene glycol 
                 50.00 
               
               
                   
                 Tamol ® 1254 AA/MAA dispersant 
                 38.16 
               
               
                   
                 Triton ® CF-10 surfactant 
                 2.00 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Kathon ® LX 1.5% biocide 
                 2.00 
               
               
                   
                 Ti-Pure ® R900 interior-grade TiO 2   
                 1335.52 
               
               
                   
                 Letdown prepared of Cowles disperser 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Water 
                 97.00 
               
               
                   
                 Letdown prepared on low speed mixer 
               
               
                   
                 Natrosol ® 250 MHR (3.5% solution in 
                 41.16 
               
               
                   
                 water) HEC thickener 
               
               
                   
                 Water 
                 48.18 
               
               
                   
                 KU initially after preparation 
                 80 
               
               
                   
                 pH initially after preparation 
                 0.6 
               
               
                   
                 ICI initially after preparation 
                 9.37 
               
               
                   
                 Brookfield viscosity 
                 15100 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale prepared (gallons) 
                 50 
               
               
                   
                   
               
             
          
         
       
     
     Example 4 
     Mixture A described below will require no mixing to remain stable. 
     
       
         
               
               
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 A 
               
               
                   
                 Ingredients 
                 lbs/100 gallons 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Grind prepared on Cowles disperser 
                   
               
               
                   
                 Water 
                 168.76 
               
               
                   
                 Propylene glycol 
                 62.5 
               
               
                   
                 Tamol ® 1254 AA/MAA dispersant 
                 26.24 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.88 
               
               
                   
                 Triton ® CF-10 surfactant 
                 2.50 
               
               
                   
                 Kathon ® LX 1.5% biocide 
                 2.50 
               
               
                   
                 Ti-Pure ® R902 universal-grade TiO 2   
                 918.2 
               
               
                   
                 Letdown prepared on Cowles disperser 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.88 
               
               
                   
                 Ropaque ® Ultra opaque polymer 
                 205.56 
               
               
                   
                 Letdown prepared on a low speed mixer 
               
               
                   
                 Natrosol ® Plus 430 (4% in solution in 
                 89.52 
               
               
                   
                 water) HMHEC thickener 
               
               
                   
                 Ammonia hydroxide (28%) 
                 0.46 
               
               
                   
                 Water 
                 55.46 
               
               
                   
                 KU initially after preparation 
                 97 
               
               
                   
                 pH initially after preparation 
                 8.77 
               
               
                   
                 ICI initially after preparation 
                 1.0 
               
               
                   
                 Brookfield viscosity 
                 18000 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale prepared (gallons) 
                 50 
               
               
                   
                   
               
             
          
         
       
     
     Example 5 
     Mixtures A to C described below will require no mixing to remain stable. 
     
       
         
               
               
               
             
               
               
               
             
               
               
               
             
               
               
               
             
               
               
               
             
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                   
                 A 
               
               
                   
                 Ingredients 
                 lbs/100 gallons 
               
               
                   
                   
               
             
          
           
               
                   
                 Grind prepared on Cowles disperser 
                   
               
               
                   
                 Water 
                 160 
               
               
                   
                 Propylene glycol 
                 50 
               
               
                   
                 Tamol ® 1124 AA/HPA dispersant 
                 7.35 
               
               
                   
                 Kathon ® LX 1.5% biocide 
                 2.00 
               
               
                   
                 Ti-Pure ® R706 universal-grade TiO 2   
                 918.2 
               
               
                   
                 Letdown prepared on Cowles disperser 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.5 
               
               
                   
                 Ropaque ® Ultra opaque polymer 
                 205.56 
               
               
                   
                 Acrysol ® RM-2020NPR HEUR 
                 40.0 
               
               
                   
                 thickener 
               
               
                   
                 Natrosol ® Plus 330 (3% in solution in 
                 68.32 
               
               
                   
                 water) HMHEC thickener 
               
               
                   
                 Ammonium hydroxide (28%) 
                 2.16 
               
               
                   
                 Water 
                 76.3 
               
               
                   
                 KU initially after preparation 
                 98 
               
               
                   
                 pH initially after preparation 
                 8.73 
               
               
                   
                 ICI initially after preparation 
                 1.3 
               
               
                   
                 Brookfield viscosity 
                 18500 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale prepared (gallons) 
                 50 
               
               
                   
                   
               
             
          
           
               
                   
                   
                 B 
               
               
                   
                 Ingredients 
                 lbs/100 gallons 
               
               
                   
                   
               
             
          
           
               
                   
                 Grind prepared on Cowles disperser 
                   
               
               
                   
                 Water 
                 130 
               
               
                   
                 Propylene glycol 
                 50 
               
               
                   
                 Tamol ® 731 MA/DIB dispersant 
                 29.38 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Triton ® CF-10 surfactant 
                 2.00 
               
               
                   
                 Kathon ® LX 1.5% biocide 
                 2.00 
               
               
                   
                 Ti-Pure ® R706 universal-grade TiO 2   
                 734.56 
               
               
                   
                 Letdown prepared on Cowles disperser 
               
               
                   
                 Rhoplex ® SG-10M acrylic binder 
                 151.20 
               
               
                   
                 Texanol ® coalescent 
                 12.5 
               
               
                   
                 Ammonium hydroxide (28%) 
                 0.60 
               
               
                   
                 Ropaque ® Ultra opaque polymer 
                 164.44 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Acrysol ® RM-2020NPR HEUR 
                 30.00 
               
               
                   
                 thickener 
               
               
                   
                 Letdown prepared on low speed mixer 
               
               
                   
                 Natrosol ® Plus 330 (3% in solution in 
                 27.6 
               
               
                   
                 water) HMHEC thickener 
               
               
                   
                 Water 
                 65.82 
               
               
                   
                 KU initially after preparation 
                 98 
               
               
                   
                 pH initially after preparation 
                 8.73 
               
               
                   
                 ICI initially after preparation 
                 1.9 
               
               
                   
                 Brookfield viscosity 
                 10800 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale prepared (gallons) 
                 50 
               
               
                   
                   
               
             
          
           
               
                   
                   
                 C 
               
               
                   
                 Ingredients 
                 lbs/100 gallons 
               
               
                   
                   
               
             
          
           
               
                   
                 Grind prepared on Cowles disperser 
                   
               
               
                   
                 Water 
                 130 
               
               
                   
                 Propylene glycol 
                 50 
               
               
                   
                 Tamol ® 731 MA/DIB dispersant 
                 30.04 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Triton ® CF-10 surfactant 
                 2.00 
               
               
                   
                 Kathon ® LX 1.5% biocide 
                 2.00 
               
               
                   
                 Kronos ® 2102 universal-grade TiO 2   
                 751.09 
               
               
                   
                 Rhoplex ® SG-10M acrylic binder 
                 151.2 
               
               
                   
                 Texanol ® coalescent 
                 12.49 
               
               
                   
                 Ammonia hydroxide (28%) 
                 0.60 
               
               
                   
                 Ropaque ® Ultra opaque polymer 
                 164.44 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.50 
               
               
                   
                 Acrysol ® RM-2020NPR HEUR 
                 30.00 
               
               
                   
                 thickener 
               
               
                   
                 Letdown prepared on low speed mixer 
               
               
                   
                 Natrosol ® Plus 330 (3% in solution in 
                 25.04 
               
               
                   
                 water) HMHEC thickener 
               
               
                   
                 Water 
                 67.76 
               
               
                   
                 KU initially after preparation 
                 99 
               
               
                   
                 pH initially after preparation 
                 1.8 
               
               
                   
                 ICI initially after preparation 
                 9.22 
               
               
                   
                 Brookfield viscosity 
                 10100 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale repared (gallons) 
                 50 
               
               
                   
                   
               
             
          
         
       
     
     Example 6 
     Mixtures A to D described below will require occasional mixing to remain stable. 
     
       
         
               
               
               
             
               
               
               
             
               
               
               
             
               
               
               
             
           
               
                   
               
             
             
               
                   
                 A 
                 B 
               
               
                 Ingredients 
                 lbs/100 gallons 
                 lbs/100 gal 
               
               
                   
               
             
          
           
               
                 Grind prepared on Cowles disperser 
                   
                   
               
               
                 Water 
                 272.7 
                 272.7 
               
               
                 Tamol ® 1124 AA/HPA dispersant 
                 7.35 
                 7.35 
               
               
                 Kathon ® LX 1.5% biocide 
                 2.00 
                 2.00 
               
               
                 Ti-Pure ® R706 universal-grade TiO 2   
                 918.2 
                 918.2 
               
               
                 Letdown prepared on low speed mixer 
               
               
                 Triton ® CF-10 surfactant 
                 0 
                 1.0 
               
               
                 Propylene glycol 
                 50 
                 50 
               
               
                 Foamaster ® VL defoamer 
                 1.5 
                 1.5 
               
               
                 Ropaque ® Ultra opaque polymer 
                 205.56 
                 205.56 
               
               
                 Natrosol ® Plus 330 (3% in solution in 
                 192 
                 113 
               
               
                 water) HMHEC thickener 
               
               
                 Attagel ® 50 attagulpite clay (100% 
                 — 
                 5.0 
               
               
                 solid) 
               
               
                 Ammonia hydroxide (28%) 
                 1.96 
                 1.98 
               
               
                 KU initially after preparation 
                 92 
                 94 
               
               
                 pH initially after preparation 
                 0.5 
                 0.5 
               
               
                 ICI initially after preparation 
                 8.87 
                 8.75 
               
               
                 Brookfield viscosity 
                 23000 
                 27700 
               
               
                 (cps at 1.25 sec −1 ) 
               
               
                 Actual scale prepared (gallons) 
                 57 
                 53 
               
               
                   
               
             
          
           
               
                   
                 C 
                 D 
               
               
                 Ingredients 
                 lbs/100 gallons 
                 lbs/100 gallons 
               
               
                   
               
             
          
           
               
                 Grind prepared on Cowles disperser 
                   
                   
               
               
                 Propylene glycol 
                 50 
                 50 
               
               
                 Water 
                 160 
                 160 
               
               
                 Tamol ® 1124 AA/HPA dispersant 
                 7.35 
                 7.35 
               
               
                 Kathon ® LX 1.5% biocide 
                 2.00 
                 2.00 
               
               
                 Ti-Pure ® R706 universal-grade TiO 2   
                 918.2 
                 918.2 
               
               
                 Letdown prepared on low speed mixer 
               
               
                 Foamaster ® VL defoamer 
                 1.5 
                 1.5 
               
               
                 Ropaque ® Ultra opaque polymer 
                 205.56 
                 205.56 
               
               
                 Natrosol ® Plus 330 (3% in solution in 
                 80.06 
               
               
                 water) HMHEC thickener 
               
               
                 Natrosol ® 250 MHR (3.5% in solution 
                   
                 134.7 
               
               
                 in water) HEC thickener 
               
               
                 Ammonium hydroxide (28%) 
                 1.80 
                 1.86 
               
               
                 Water 
                 106.7 
                 50.22 
               
               
                 KU initially after preparation 
                 94 
                 98 
               
               
                 pH initially after preparation 
                 8.68 
                 8.67 
               
               
                 ICI initially after preparation 
                 0.5 
                 0.8 
               
               
                 Brookfield viscosity 
                 18700 
                 28200 
               
               
                 (cps at 1.25 sec −1 ) 
               
               
                 Actual scale prepared (gallons) 
                 50 
                 50 
               
               
                   
               
             
          
         
       
     
     Example 7 
     Mixtures A to E described below will require occasional mixing to remain stable. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                 A 
                 B 
                 C 
                 D 
                 E 
               
               
                   
                 lbs/100 
                 lbs/100 
                 lbs/100 
                 lbs/100 
                 lbs/100 
               
               
                 Ingredients 
                 gallons 
                 gallons 
                 gallons 
                 gallons 
                 gallons 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Grind pre- 
                   
                   
                   
                   
                   
               
               
                 pared on 
               
               
                 Cowles dis- 
               
               
                 perser 
               
               
                 Water 
                 115 
                 115 
                 115 
                 115 
                 93.46 
               
               
                 Propylene 
                 50 
                 50 
                 50 
                 50 
                 40.64 
               
               
                 glycol 
               
               
                 Tamol ® 
                 20.99 
                 10.49 
                 31.48 
                 41.97 
                 25 59 
               
               
                 1254 AA/ 
               
               
                 MAA 
               
               
                 dispersant 
               
               
                 Foamaster ® 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
                 2.44 
               
               
                 VL defoamer 
               
               
                 Triton ® 
                 1.50 
                 1.50 
                 1.50 
                 1.50 
                 1.63 
               
               
                 CF-10 
               
               
                 surfactant 
               
               
                 Kathon ® 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
                 1.63 
               
               
                 LX 1.5% 
               
               
                 biocide 
               
               
                 Ti-Pure ® 
                 734.56 
                 734.56 
                 734.56 
                 734.56 
                 596.96 
               
               
                 R706 univer- 
               
               
                 sal-grade 
               
               
                 TiO 2   
               
               
                 Foamaster ® 
                 1.50 
                 1.50 
                 1.50 
                 1.50 
               
               
                 VL defoamer 
               
               
                 Ropaque ® 
                 164.44 
                 164.44 
                 164.44 
                 164.44 
                 133.64 
               
               
                 Ultra opaque 
               
               
                 polymer 
               
               
                 Letdown 
               
               
                 prepared on 
               
               
                 low speed 
               
               
                 mixer 
               
               
                 Res 3083 
                 140.10 
                 140.10 
                 140.10 
                 140.10 
                 245.05 
               
               
                 emulsion 
               
               
                 Texanol ® 
                 11.37 
                 11.37 
                 11.37 
                 11.37 
                 15.73 
               
               
                 coalescent 
               
               
                 Acrysol ® 
                 9.6 
                 7.12 
                 5.67 
                 4.12 
                 7.92 
               
               
                 DR-3 HASE 
               
               
                 thickener 
               
               
                 Ammonium 
                 2.12 
                 2.34 
                 1.96 
                 1.81 
                 2.28 
               
               
                 hydroxide 
               
               
                 (28%) 
               
               
                 Water 
                 150.8 
                 152.8 
                 145.55 
                 138.67 
                 144.93 
               
               
                 KU initially 
                 100 
                 101 
                 99 
                 97 
                 98 
               
               
                 after 
               
               
                 preparation 
               
               
                 pH initially 
                   
                 8.69 
                 8.54 
                 8.68 
                 8.4 
               
               
                 after 
               
               
                 preparation 
               
               
                 ICI initially 
                 0.9 
                 0.8 
                 0.8 
                 0.7 
                 1.1 
               
               
                 after 
               
               
                 preparation 
               
               
                 Brookfield 
                 27700 
                 29200 
                 31600 
                 29900 
                 23800 
               
               
                 viscosity 
               
               
                 (cps at 1.25 
               
               
                 sec −1 ) 
               
               
                   
               
             
          
         
       
     
     Example 8 
     Mixtures A and B described below will require constant mixing to remain stable. 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 A 
                 B 
               
               
                   
                   
                 lbs/100 
                 lbs/100 
               
               
                   
                 Ingredients 
                 gallons 
                 gallons 
               
               
                   
                   
               
             
             
               
                   
                 Grind prepared on Cowles disperser 
                   
                   
               
               
                   
                 Water 
                 174.98 
                 174.98 
               
               
                   
                 Propylene glycol 
                 62.49 
                 62.49 
               
               
                   
                 Tamol ® 731 MA/DIB dispersant 
                 36.72 
                 36.72 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.87 
                 1.87 
               
               
                   
                 Triton ® CF-10 surfactant 
                 2.50 
                 2.50 
               
               
                   
                 Kathon ® LX 1.5% biocide 
                 2.50 
                 2.50 
               
               
                   
                 Ti-Pure ® R706 universal-grade TiO 2   
                 918.12 
                 918.12 
               
               
                   
                 Letdown prepared on Cowles disperser 
               
               
                   
                 Foamaster ® VL defoamer 
                 1.87 
                 1.87 
               
               
                   
                 Ropaque ® Ultra opaque polymer 
                 205.53 
                 205.53 
               
               
                   
                 Letdown on a low speed mixer 
               
               
                   
                 Natrosol ® Plus 330 (3% in solution in 
                   
                 45.09 
               
               
                   
                 water) HMHEC thickener 
               
               
                   
                 Natrosol ® 250 MHR (3.5% in solution 
                 127.69 
                 45.09 
               
               
                   
                 in water) HEC thickener 
               
               
                   
                 Ammonium hydroxide (28%) 
                 1.00 
                 1.34 
               
               
                   
                 Water 
                 0 
                 80.99 
               
               
                   
                 KU initially after preparation 
                 99 
                 99 
               
               
                   
                 pH initially after preparation 
                 8.69 
                 8.76 
               
               
                   
                 ICI initially after preparation 
                 1.6 
                 0.8 
               
               
                   
                 Brookfield viscosity 
                 20200 
                 22700 
               
               
                   
                 (cps at 1.25 sec −1 ) 
               
               
                   
                 Actual scale prepared (gallons) 
                 100 
                 100 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
             
           
               
                   
               
               
                 Supplier Information 
               
             
          
           
               
                 Material Name 
                 Description 
                 Supplier 
               
               
                   
               
               
                 Tamol ™ 1124 
                 Dispersant 
                 Rohm and Haas Company 
               
               
                   
                   
                 (Philadelphia, PA) 
               
               
                 Tamol ™ 1254 
                 Dispersant 
                 Rohm and Haas Company 
               
               
                   
                   
                 (Philadelphia, PA) 
               
               
                 Tamol ™ 731 
                 MA/GIB Dispersant 
                 Rohm and Haas Company 
               
               
                   
                   
                 (Philadelphia, PA) 
               
               
                 Acrysol ™ DR-1 
                 HASE Thickener 
                 Rohm and Haas Company 
               
               
                   
                   
                 (Philadelphia, PA) 
               
               
                 Acrysol ™ DR-3 
                 HASE 
                 Rohm and Haas Company 
               
               
                   
                 Thickener/Rheology 
                 (Philadelphia, PA) 
               
               
                   
                 Modifier 
               
               
                 Acrysol ™ DR-73 
                 HASE Thickener 
                 Rohm and Haas Company 
               
               
                   
                   
                 (Philadelphia, PA) 
               
               
                 Acrysol ™ RM-2020 
                 HEUR 
                 Rohm and Haas Company 
               
               
                 NPR 
                 Thickener/Rheology 
                 (Philadelphia, PA) 
               
               
                   
                 Modifier 
               
               
                 Rhoplex ™ SG-10M 
                 Emulsion Polymer 
                 Rohm and Haas Company 
               
               
                   
                 Binder 
                 (Philadelphia, PA) 
               
               
                 RES 3083 
                 Emulsion Polymer 
                 Rohm and Haas Company 
               
               
                   
                 Binder 
                 (Philadelphia, PA) 
               
               
                 Kathon ™ LX 1.5% 
                 Biocide 
                 Rohm and Haas Company 
               
               
                   
                   
                 (Philadelphia, PA) 
               
               
                 Triton ™ CF-10 
                 Surfactant 
                 Union Carbide Corporation 
               
               
                   
                   
                 (Danbury, CT) 
               
               
                 Foamaster ™ VL 
                 Defoamer 
                 Henkel Corporation (King 
               
               
                   
                   
                 of Prussia, PA) 
               
               
                 Ti-Pure ™ R-706 
                 Titanium Dioxide 
                 E. I. Dupont de Nemours 
               
               
                   
                   
                 and Co., Inc. 
               
               
                   
                   
                 (Wilmington, DE) 
               
               
                 Ti-Pure ™ R-900 
                 Titanium Dioxide 
                 E. I. Dupont de Nemours 
               
               
                   
                   
                 and Co., Inc. 
               
               
                   
                   
                 (Wilmington, DE) 
               
               
                 Ti-Pure ™ R-902 
                 Titanium Dioxide 
                 E. I. Dupont de Nemours 
               
               
                   
                   
                 and Co., Inc. 
               
               
                   
                   
                 (Wilmington, DE) 
               
               
                 Kronas ® 2102 
                 Universal Grade 
                 Kronas (Houston, TX) 
               
               
                   
                 Titanium Dioxide 
               
               
                 Ropaque ® 
                 Ultra Opaque 
                 Rohm and Haas 
               
               
                   
                 Synthetic/Polymer 
                 (Philadelphia, PA) 
               
               
                 Texanol ™ 
                 Coalescent 
                 Eastman Chemical 
               
               
                   
                   
                 (Kings Port, TN) 
               
               
                 Natrosol ® 
                 HEC Thickner 
                 Hercules (Wilmington, DE) 
               
               
                 Natrosol ® Plus 430 
                 HMHEC Thickener 
                 Hercules (Wilmington, DE) 
               
               
                 Natrosol ® Plus 330 
                 HMHEC Thickener 
                 Hercules (Wilmington, DE) 
               
               
                 Natrosol ® 250 MHR 
                 HEC Thickener 
                 Hercules (Wilmington, DE) 
               
               
                 Attrgel ® 50 
                 Attapulgite Clay 
                 Engelhardt (Edison, NJ)