IMPROVED PROCESS FOR THE MANUFACTURE OF

ORGANOSILICON COMPOUND-TREATED PIGMENTS, AND COATING

COMPOSITIONS EMPLOYING THE SAME

This invention relates to an improved method of surface-treated titanium dioxide pigment manufacture utilizing organosilicon compounds and to the use of certain of the resulting titanium dioxide pigments in aqueous coating compositions.

Inorganic pigments are used as opacifiers and colorants in many industries including the coatings, plastics, and paper industries. In general, the effectiveness of the pigment in such applications depends on how evenly the pigment can be dispersed in a coating, in plastic or in paper. In this regard, it is known that the wetting and dispersing properties of titanium dioxide pigments can be improved by exposure to certain inorganic treatments, for example, depositing inorganic metal oxide and/or metal hydroxide coatings on the surface of the titanium dioxide. In addition, certain other chemical modifications of titanium dioxide pigment surfaces, involving treatment with organic compounds, are also known to improve pigment performance.

With regard to the present invention, it is, in particular, known to treat titanium dioxide pigment surfaces with organosilicon compounds. Organosilicon compound surface treatments provide a number of desirable benefits, but are especially of interest for their non-migrating character as they react with and are bound to the pigment surface. The most advantageous organosilicon treatment in more general terms will depend on what particular end-use is intended for the surface-treated pigment, whether in thermoplastics, coatings or in paper. Accordingly, many patents have been issued

disclosing methods for improving titanium dioxide pigments wherein an organosilicon compound is deposited onto the pigment surface prior to its incorporation into such end use materials as plastics, and to a lesser extent in coatings, inks and paper.

For example, U.S. Patent 3,132,961 discloses a process for rendering finely divided non-alkaline filler material hydrophobic by contacting said finely divided filler material with a diorganopolysiloxane in the presence of an acid. Among the filler materials described are silica, clay, iron oxides, and titanium dioxide.

U.S. Patent 4,061,503 discloses the treatment of particulate titanium dioxide with a polyether substituted silicon compound which serves to enhance its employment in pigmented and/or filled paints and plastics, and in reinforced plastic composite compositions.

U.S. Patent 4,151,154 discloses compositions comprising inorganic particles containing on their surfaces a silane, its hydrolyzates or resulting condensates, which silane possesses at least two to about three hydrolyzable groups bonded to the silicon thereof and an organic group which contains a polyalkylene oxide group. These modified inorganic particles exhibit enhanced performance in pigmented and/or filled paints and plastics, and in reinforcing plastic composite structures.

U.S. Patent 4,375,989 discloses improved dispersibility of a titanium dioxide pigment by coating the pigment with an organic coating selected from the group comprising large-molecule fatty acids and their salts; organic silicon compounds, such as dimethyl polysiloxane; alcohols and polyalcohols. The titanium dioxide pigment also comprises a coating of an inorganic substance.

U.S. Patent 4,810,305 describes a modified hydrophobic colored or magnetic

pigment or filler comprising a hydrophobic pigment or filler containing a surface treatment derived from an organopolyhydrosiloxane. Compositions include titanium dioxide pigments and are useful as pigments or fillers in synthetic resins.

U.S. Patent 4,801,445 and U.S. Patent 4,882,225 are directed toward cosmetics compositions containing modified powders or particulate materials having a silicone polymer film coated on substantially the entire surface, said silicone polymer being derived from at least one silicone compound containing an Si-H group.

U.S. Patent 4,935,063 discloses inorganic fillers or pigments having simultaneous reinforcing effect and stabilizing effect on organic polymers obtained by a process comprising bringing the inorganic filler or pigment into contact with a solution, in an inert organic solvent, of a sterically hindered amine comprising one or more alkoxysilane groups in its molecule, maintaining the obtained mixture at higher than ambient temperature for a period of at least 0.5 hours, removing the solvent, and recovering the stabilizing filler or pigment obtained.

U.S. Patent 5,035,748 describes an inorganic pigment comprising a content of at least 0.1% by weight and at most 5% by weight of one or more polyorganosiloxanes, wherein the polyorganosiloxanes have viscosities of 10 to 100,000 mPa.s and a relative molecular weight of 500 to 500,000, have no reactive or crosslinking groups, contain at least one C ₉ -C ₂ S Si-alkyl and/or one C ₉ -C ₂ 5 Si-aryl group per molecule, the total content of these groups in the polyorganosiloxane being 7-70% by weight and the other organic radicals contained in the polyorganosiloxane having 1 to 8 carbon atoms. These pigments can be used in laquers, emulsion paints, plastics, toners, magnetic recording materials, building materials, and enamels.

U.S. Patent 5,501,732 discloses an improved process for preparing silanized titanium dioxide pigment for plastic and coating applications using a titanium dioxide slurry as a feedstock, wherein the viscosity of the high solids titanium dioxide slurry is reduced by adjusting the pH of the slurry in the range of about 7.5 to about 11.

U.S. Patent 5,607,994, U.S. Patent 5,631,310, U.S. Patent 5,889,090, and U. S. Patent 5,959,004 claim processes and compositions relating to white-pigmented polymers (particularly, polyolefins such as polyethylene) containing white pigments treated with at least one silane or a mixture of at least one silane and at least one polysiloxane resulting in improved processibiliry in thermoplastics compounding and improved performance properties, such as lacing resistance, in a polymeric matrix. Preferred silanes compounds are alkyl trialkoxysilanes.

U.S. Patent 6,133,360 discloses thermoplastic resin compositions containing an aromatic polycarbonate resin and a surface modified titanium dioxide having a first coating and no further coatings. Preferred titanium dioxide first coating materials are polyols or polysiloxanes. The thermoplastic resin compositions exhibit improved resistance to streaking compared to such thermoplastic resin compositions which incorporate titanium dioxide having a first coating and at least one additional coating.

U.S. Patent 6,455,158 Bl relates to the silanization or surface treatment of minerals with alkylsilanes and alkylsilane copolymers and to alkylsilane copolymers useful for surface treating pigments or fillers. The alkylsilane copolymers comprise at least two different monomers and find utility for the surface treatment of white pigments, such as titanium dioxide, for improving the dispersibility and processibiliry of the pigments when compounded with a polymeric material such as polyolefins.

U.S. Patent Application Publication No. US 2002/0172697 Al describes a metal oxide-organopolysiloxane hybrid powder, a method for the preparation thereof, and a cosmetic composition containing said powder.

U.S. Patent Application Publication No. US 2003/0027896 Al discloses a surface modified inorganic oxide powder having a surface modified with a mixed solution, which includes an organopolysiloxane and a silane compound. The resulting powders improve reinforcement of polar resins.

U.S. Patent 6,770,327 discloses aminoalkylalkoxy silane mixtures comprising optionally, alkyl or hydroxyalkyl-functionalized siloxanes, to processes for preparing said mixtures, and to their use as reinforcing agents, surface modifying agents, or in coatings.

U.S. Patent 6,841,197 discloses oligomer mixtures of n-propylethoxy silanes, to processes for preparing said mixtures, and to their use as reinforcing agents, surface modifying agents, or in coatings.

DE 197 51 857 Al describes a method for producing phosphonatosiloxane-treated inorganic particles by incorporating organophosphonate compounds into organosiloxane compounds, such compounds being useful in plastics applications.

European Patent Specification EP 1 065 234 Bl relates to novel silicones for powder treatment, powders having the surface treated with such silicones, and cosmetic materials containing such surface-treated powders, wherein the surface treatment imparts to the powder a high affinity for fats and oils, including ester oils, glycerides, silicone oils, and fluorinated oils.

European Patent Specification EP 1 424 373 A2 relates to hydrophilized powders wherein the powder surface is treated with a polyether-modified silicone, and to their application in cosmetics, coatings, and inks.

U.S. Patent Application Publication No. US 2005/0129602 Al discloses a process for production of titanium dioxide pigment and resin compositions comprising coating the hydrolysis product of an alkylsilane compound containing at least one C ₆ Ho group by dry processing on surfaces of particles of titanium dioxide.

From the citations given above it is clear that many uses of organosilicon compound-treated pigments have been documented. However, in none of the references cited above are processes disclosed which describe aqueous treatment of pigments with alkyltrialkoxysilanes and dialkyldialkoxysilanes at pH values of between about 3.5 and about 7 in the presence of monoprotic acids. Alkyltrialkoxysilanes and dialkyldialkoxysilanes tend to oligomerize and crosslink to a lesser extent in this pH range and so are more effectively and easily applied to a titanium dioxide pigment as a surface treatment. Nevertheless, the slow rate of reaction of alkyltrialkoxysilanes and dialkyldialkoxysilanes in this pH range tends also to lead to undesired increases in manufacturing cycle-time, perhaps providing an explanation for the comparative absence of art pertaining to the surface treatment of titanium dioxide pigments with organosilicon compounds in this mildly acidic pH range.

Prior to treatment with organosilicon compounds, rutile titanium dioxide is commonly produced from titanium tetrachloride using vapor phase oxidation processes as disclosed in any number of patents and other printed publications, for example, in U.S. Patents 3,208,866, 3,512,219, 5,840,112, 6,207,131 and 6,350,427. The reaction effluent

from these vapor phase oxidation systems is generally cooled immediately upon leaving the reaction chamber, yielding a solid, agglomerated titanium dioxide intermediate.

This intermediate typically undergoes further processing steps in order to provide a finished product suitable for the uses listed above, including:

(1) dispersing the intermediate (or crude) material in an aqueous medium using a dispersing agent such as a polyphosphate,

(2) wet milling the resulting slurry to achieve a reduced particle size,

(3) precipitating inorganic oxides such as silica or alumina onto the particle surfaces of the wet milled titanium dioxide slurry,

(4) recovering the alumina- and/or silica-treated titanium dioxide pigment from the aqueous slurry by filtration,

(5) washing the filtered product to remove residual salts and impurities,

(6) drying the washed filtered product, and

(7) dry-milling the dried pigment using a fluid energy mill.

The deposition of inorganic oxides according to step (3), such as with silica or alumina onto the wet-milled titanium dioxide, is known to provide some desired pigment end-use properties as well as enabling the pigment to be recovered ^* and washed using conventional vacuum-type and/or pressure-type filtration systems during manufacture.

For example, silica is typically added to impart improved resistance to the deleterious effects of ultraviolet light in pigmented end-use applications, whereas alumina is typically added to ensure smooth processing through filtration, drying, and fluid energy milling. Unfortunately, in some cases the presence of the inorganic oxides has also been observed to reduce the dispersibility of the dry pigment in coatings and

thermoplastics so that as an alternative to added alumina, for instance, polymeric flocculants and/or multivalent metal ion flocculating salts have been added to the wet milled titanium dioxide dispersion in order to enable the pigment to still be collected and recovered using conventional vacuum-type and/or pressure-type filtration systems. However, the polymeric flocculants frequently themselves detract from the performance of the processed titanium dioxide product.

When spray drying is used to dry the titanium dioxide material following step (5), the washed titanium dioxide material is typically diluted with additional carrier liquid to enable delivery of the titanium dioxide material slurry to the spray dryer system as a fluid rather than a semi-solid. This dilution step, while enabling more practical and consistent conveyance of the semi-solid material to the spray dryer itself, can result in slower spray dryer throughput rates due to the presence of the additional carrier medium, as well as higher energy costs associated with the removal of the larger quantities of carrier liquid.

One attempt to provide an improvement to this situation, wherein the washed titanium dioxide material, often referred to as "press cake" or "filter cake", is converted into a low viscosity slurry via the addition of an alkalinizing agent, is described in U.S. Patent Application Publication No. US 2006/0045841 Al. In this particular case, the low viscosity slurry enables the efficient spray drying of titanium dioxide pigment intermediate while at the same time providing a pigment with improved processibility when formulated into thermoplastics. However, the usefulness of the disclosed viscosity reduction process is explicitly restricted to pigments wherein substantially no inorganic oxides have been deposited on the titanium dioxide material to be spray-dried.

Several references describe alternate methods for rendering pigment press cake or

filter cake into a low viscosity fluid:

U.S. Patent 4,186,028 describes improved fluid aqueous pigment dispersions, including titanium dioxide dispersions, comprising employment of a phosphonocarboxylic acid or salt thereof as a dispersion aid. In one particularly preferred embodiment, filter cakes which are normally difficult to transport are liquified by the addition of phosphonocarboxylic acids and transported in thin form to a drying or calcining unit to save energy costs.

U.S. Patent 4,599,114 describes the treatment of titanium dioxide and other pigments with a surfactant compound consisting of the reaction product of a diamine, a carboxylic acid, and a fatty acid, to enhance the performance of the pigment in paints, plastics, paper making compositions, and reinforced plastic composite compositions. In one example, titanium dioxide press cake is converted into slurry form via vigorous mixing of the press cake with the inventive surfactant compound.

Lastly, U.S. Patent 6,139,617 discloses an improved titanium dioxide pigment exhibiting improved gloss and dispersibility in surface coatings comprising titanium dioxide having deposited thereon a treating agent comprising at least one amine salt of a monoprotic acid.

Despite all the work and effort evidenced in the prior art relating to the development of improved organosilicon compound surface treatments for pigments, or relating to the development of improved processes for the manufacture of organosilicon compound-treated pigments, further improvements are continually being sought both in the processes of manufacturing such pigments as well as in the pigments themselves in

regard to their intended uses, for example, in the aqueous coating compositions contemplated by the present invention.

The present invention provides in a first aspect a unique advancement in the process for applying an organosilicon compound surface treatment to a titanium dioxide pigment, so that an alkyltrialkoxysilane and/or dialkyldialkoxysilane surface treatment can be applied under the mildly acidic conditions preferred for enhancing the "pot-life" of these reactive materials but with a sufficient rate of reaction to provide a commercially practical manufacturing cycle-time. In a further aspect, the present invention in preferred embodiments also provides an advancement in the fluidization and efficient spray-drying of pigment press cake (or filter cake) which is thereby able to employ an inorganic surface treatment preferred for many end uses (but which had heretofore entailed substantial dilution of the press cake before spray-drying), in addition to the aforementioned organosilicon compound surface treatment. In still a further aspect, the invention provides improved aqueous coating compositions comprised of certain of the alkyltrialkoxysilane and/or dialkyldialkoxysilane-treated titanium dioxide pigments, water and a film-forming component.

An improved process for manufacturing an organosilicon-treated titanium dioxide pigment according to the present invention comprises:

(a) forming a mixture comprising a titanium dioxide material in water, said titanium dioxide material having been produced by a reaction process including a vapor phase oxidation step and wherein, other than any inorganic oxides formed in said reaction process along with said titanium dioxide material, substantially no inorganic oxides have been deposited on said titanium dioxide material;

(b) wet milling said mixture;

(c) after step (b), optionally depositing on said wet milled titanium dioxide material one or more inorganic oxides selected from the oxides of aluminum, boron, cerium, phosphorus, silicon, tin, titanium and zirconium;

(d) adjusting the pH of the slurry resulting from steps (b) or (c) to a value of from 5.0 to 8.5, in order to flocculate said titanium dioxide material whereby the titanium dioxide material may be recovered by vacuum or pressure filtration;

(e) after step (d), removing said titanium dioxide material from said mixture by vacuum or pressure filtration;

(f) after step (e), washing said titanium dioxide material;

(g) after step (f), converting said washed titanium dioxide material to a fluid dispersion having a mildly acidic pH value of 3.5 and greater (but being less than 7) via addition of a fluidizing agent comprising a water-soluble monoprotic acid, optionally and preferably without substantial dilution of the titanium dioxide material;

(h) after, or concurrently with, step (g), adding to the resulting dispersion of titanium dioxide material an organosilicon compound, with mixing;

(i) after step (h), spray drying the dispersion of the washed titanium dioxide material resulting from step (h) to yield a dry titanium dioxide pigment powder.

The resulting dry, organosilicon compound surface-treated titanium dioxide pigment powder optionally and preferably is then post-processed in a fluid energy mill in the presence or absence of additional functional additives known to the art, to finally yield a dry finished pigment product that is suited for incorporation in coatings, in paper or in plastics as desired. Alternatively, the dry, organosilicon compound surface-treated

titanium dioxide pigment powder, optionally without but preferably with steam micronization of the pigment powder, can then be combined with a fluid medium in the presence or absence of known functional additives, utilizing methods known to the art, to yield a finished pigment slurry adapted for a desired end use, for example, in coatings or in paper, but especially in aqueous coating compositions.

As has been discussed previously, the alkyltrialkoxysilanes and dialkyldialkoxysilanes would for ease of handling and application ideally be applied to titanium dioxide pigments at a mildly acidic pH, namely, a pH of 3.5 and greater but being less than 7, precisely according to step (g) above. However, the slow reaction rate and resulting long manufacturing cycles associated with application of these materials under these conditions have heretofore proven an impediment in the surface treating of titanium dioxide pigments. The present invention is based, in its process aspects, upon the discovery that by spray drying a high solids dispersion of filter cake, as enabled by the use of monoprotic acid fluidizing agents even where the pigment in question has incorporated a treatment of one or more inorganic oxides according to step (c), sufficient heat is provided through the spray drying step to effectively promote the desired bonding of the alkyltrialkoxysilane and dialkyldialkoxysilane surface treatments with the pigment surface and reduce the manufacturing cycle time for the pigments to a commercially practical cycle time. Where fluid energy milling (or micronization) is performed in an optional further step, the heat supplied through the micronization of the spray-dried organosilicon compound-treated titanium dioxide can be further used to advance the reaction. In this instance, it will be appreciated that the fluidization of the filter cake can be accompanied with a degree of dilution as needed or as considered appropriate, which

would be compensated for by the additional heat of micronization. A more complete reaction of the organosilicon compounds with the surface of the titanium dioxide pigment is seen in turn in improved gloss and tint strength properties when the titanium dioxide pigments produced by the present invention are formulated into coalings systems.

Obviously, apart from the beneficial effect noted on the utility of the alkyltrialkoxysilane and dialkyldialkoxysilane surface treatment materials for treating titanium dioxide pigments, fluidization of the filter cake with one or more monoprotic acids provides benefits generally in enabling the spray drying step to be carried out without a substantial dilution of the titanium dioxide material, even in the presence of one or more inorganic oxides as are desirably added to the titanium dioxide material in many cases for providing wanted end use properties. A higher solids content for the dispersion on spray drying means higher product throughput rates. In addition, substantially less heat energy is required in producing a certain quantity of pigment, since less water is required to be removed from the higher solids feed - reducing the processing costs per ton of pigment produced. For all dispersion solids, the use of low viscosity spray dryer feeds results in pigment with inherently less residual moisture without having to raise the drying temperature.

In general, any type of titanium dioxide material can be processed in accordance with the instant invention. Preferred is rutile titanium dioxide material. Most preferred is rutile titanium dioxide which has been produced from titanium tetrachloride using a vapor phase oxidation step. The titanium dioxide material can also contain an amount of alumina, from aluminum chloride which has been conventionally added as a rutilization aid during the vapor phase oxidation step along with the titanium tetrachloride. Other

inorganic oxides formed during the oxidation step may be present as well, to the extent one skilled in the art may wish to incorporate other oxidizable inorganic materials in the oxidation step as has been described or suggested elsewhere for various purposes, for example, particle size control; see, for instance, U.S. Patents 3,856,929, 5,201,949, 5,922,120 and 6,562,314.

The system used in the wet milling step of the inventive method can be a disk- type agitator, a cage-type agitator, or generally any other type of wet milling system commonly used in the art. The milling media employed can be sand, glass beads, alumina beads, or generally any other commonly used milling media. The individual grains, particles, or beads of the milling media will preferably be denser than the aqueous slurry used in forming the titanium dioxide dispersion.

Following the wet milling step, an inorganic coating is optionally applied utilizing any of the known processes to effect deposition of inorganic oxides onto the titanium dioxide. The particular inorganic oxides applied and the manner of their application are not critical, and various possibilities are well known to those skilled in the art, so further detail on this aspect is not necessary. By way of example of known inorganic oxide treatment protocols, for coatings end-use applications U. S. Patents 5,203,916 and 5,976,237 describe inorganic treatment protocols.

The pH of the titanium dioxide dispersion is then adjusted to cause the titanium dioxide material to flocculate. Preferably, a sufficient amount of an acid or base is added to the dispersion during this step to bring the pH of the dispersion to a value in the range of from 5 to 9. Most preferably, the pH of the dispersion is adjusted during this step to a value of at least 5.5 up to 8.

The flocculated titanium dioxide is then filtered using a vacuum-type filtration system or a pressure-type filtration system and is washed. At this point, the washed normally solid or semi-solid titanium dioxide material, typically having a titanium dioxide solids content of from 40 percent to 70 percent by weight and a Brookfield viscosity of more than 10,000 cps, is converted to a fluid dispersion via the direct addition of a fluidizing agent, with mixing. Preferably the viscosity of the resulting titanium dioxide slurry is reduced to a value of less than 1000 cps. More preferably the viscosity of the titanium dioxide slurry is reduced to a value of less than 500 cps; most preferably to a value of less than 100 cps.

The fluidizing agent is preferably added as a dilute aqueous solution, preferably being 25 percent or less in concentration of the fluidizing agent. The preferred final concentration of the fluidizing agent after addition to the washed titanium dioxide is between 0.025% by weight and 2% by weight based on the titanium dioxide material. More preferred concentrations of fluidizing agent are between 0.05% by weight and 1% by weight based on the titanium dioxide material. Most preferred concentrations of fluidizing agent are between 0.10% by weight and 0.5% by weight based on the titanium dioxide material.

Suitable fluidizing agents for the purpose of converting the washed titanium dioxide intermediate into a fluid dispersion are selected from the water-soluble monoprotic acids. Exemplary water-soluble monoprotic acids include nitric acid, hydrochloric acid, and carboxylic acids, sulfonic acids, phosphoric acid diesters and phosphinic acids containing fewer than eight carbon atoms, and combinations of one or more of the foregoing. Preferred examples include formic acid, acetic acid, propionic

acid, lactic acid, glycolic acid, methanesulfonic acid, p-toluenesulfonic acid, phosphoric acid dimethyl ester, methylphosphonic acid monomethyl ester, dimethylphosphinic acid, hydrochloric acid and nitric acid. The term "water-soluble" as used herein in referring to the water-soluble monoprotic acids means that the acid in question has a solubility in water at room temperature of 0.20% by weight of solution or greater.

Suitable organosilicon compounds comprise not only the aforementioned preferred alkyltrialkoxysilanes and/or dialkyldialkoxysilanes, but also the oligomers of these, mixtures of the oligomers, and the copolymers and co-oligomers of said alkoxysilanes. Generally, the alkyltrialkoxysilanes and dialkyldialkoxysilanes will contain (apart from the context of the improved aqueous coating compositions described more particularly below) from three carbon atoms up to twenty-eight carbon atoms, though preferably the alkyltrialkoxysilanes and dialkyldialkoxysilanes will contain from three to four carbon atoms up to from fourteen to eighteen carbon atoms, depending on the intended end use for the pigments. Although not considered material to the practice of the instant invention, polymethylhydrogensiloxanes may also be used in combination with the aforementioned alkyltrialkoxysilanes and dialkyldialkoxysilanes and the oligomers thereof, without departing from the spirit and scope of the claims.

The resulting aqueous dispersion of titanium dioxide is spray dried to produce a dry titanium dioxide pigment powder. The dry product thus produced can be conventionally ground to a desired final particle size distribution using, for example, steam micronization in the presence or absence of additional functional additives as known in the art.

Alternatively, the resulting pigment powder can be converted into a fluid slurry,

typically an aqueous slurry, utilizing any of the various methods known in the art. Especially, an aqueous coating composition can be formed from the spray-dried pigment.

In this last respect, an improved, higher tint strength and gloss coating composition according to the present invention comprises water, a film-forming component and at least one inorganic pigment surface treated with one or more organosilicon compounds from the alkyltrialkoxysilanes and dialkyldialkoxysilanes and mixtures, oligomers and copolymers of the alkyltrialkoxysilanes and dialkyldialkoxysilanes, wherein the alkyl groups contain from three to six carbon atoms (preferably containing three carbon atoms) and optionally contain an oxygen atom or contain fluorine and/or chlorine heteroatoms. Conventionally such alkyl groups impart hydrophobic characteristics, but by controlling and limiting the amounts used of these organosilicon treatments in an aqueous coating composition according to the present invention, the dispersibility in the composition of a conventionally hydrophilic inorganic pigment such as titanium dioxide is not materially adversely affected, but improvements are at the same time afforded in terms of the compatibility of the pigment with the film- forming component, typically being a water-soluble or water-dispersible, polymeric binder material, as demonstrated by improved tint strength and gloss properties.

The pigmented aqueous coating compositions of the present invention may otherwise contain any other components which have been known or commonly used in the known pigmented aqueous coating compositions, for example, rheology modifiers, biocides, wetting agents, dispersants, coalescing agents and other fillers.

Surprisingly, it has been found that only a very narrow range of carbon atoms in the alkyl group is useful for the instant invention. For the usually preferred circumstance

wherein the only organic surface treatments of the inorganic pigment are accomplished by means of the above-described organosilicon materials, experimental results demonstrate that when the number of carbon atoms in the alkyltrilakoxysilane or dialkyldialkoxysilane alkyl groups is greater than six, the pigments become too difficult to disperse in water-borne coatings, and when the alkyl groups contain only one or two carbon atoms there is no beneficial effect observed in the performance of the coating composition. Those skilled in the art of aqueous coating compositions will appreciate, however, that other known organic surface treatment materials may be used with these organosilicon surface treatment materials, if desired. Exemplary known inorganic pigment-containing aqueous coating systems into which the organosilicon-treated pigments of the present invention may be employed are described in United States Patents No. 6,969,734, 6,869,996, 6,762,230 and 6,646,058.

The amount of organosilicon material added as a surface treatment according to the instant invention will be an amount sufficient to provide a treated inorganic particulate-containing coating composition with improved performance properties over that of a coating composition with improved performance properties over that of a coating composition derived from the corresponding untreated inorganic particulate, which is again preferably titanium dioxide. Preferably the organosilicon surface ^• treatment comprises from 0.1 to 5 weight percent of the total weight of the treated titanium dioxide pigment, more preferably comprising from 0.25 to 2.5 percent by weight of the treated pigment and most preferably being from 0.5 to 1.5 percent of the treated pigment by weight.

The following examples serve to illustrate specific embodiments of the instant

invention without intending to limit or restrict the scope of the invention as disclosed herein. Concentrations and percentages are by weight unless otherwise indicated.

Example 1

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.8% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to about 9.5 and above, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer (Microtrac Inc. Montgomeryville, PA). The slurry was heated to 60 ⁰ C, acidified to a pH of 2.0 using concentrated sulfuric acid, then treated with 1% alumina, added rapidly as a 357 gram/liter aqueous sodium aluminate solution over a five minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to further digestion for 15 minutes at 6O ⁰ C. After this, adjustment of the pigment slurry pH to a value of 6.2 using 20% by weight aqueous sodium hydroxide solution was followed by digestion for an additional 15 minutes at 60 ⁰ C, with final readjustment of the pH to 6.2, if necessary. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re-dispersed in water

with agitation, in the presence of 0.25 % by weight based on pigment of acetic acid as a fluidizing agent, to yield a 60 % solids aqueous titanium dioxide dispersion having a pH of 4.4. The dispersion viscosity was found to be 50 cps, as determined utilizing a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm) (Brookfield Engineering Labs, Inc. Stoughton, MA).

A 1% aliquot by weight based on pigment of hexyltrimethoxysilane was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was then spray dried using an APV Nordic PSD52 Spray Dryer (Invensys APV Silkeborg, Denmark), maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. For one thousand grams of pigment the time required to carry out the spray drying and simultaneous hexyltrimethoxysilane treatment step was fifteen minutes. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the fluidizing agent. As a result, the titanium dioxide dispersion had to be diluted with water to a solids content of less than 40 % in order to lower the viscosity sufficiently to enable pumping to the spray dryer. At 38 % solids, the viscosity of the aqueous titanium dioxide dispersion was found to be 1480 cps, as measured on a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm), with a dispersion pH of 7.8. For one thousand grams of pigment the time required to carry out the spray drying and simultaneous hexyltrimethoxysilane treatment step was forty-five

minutes, as opposed to the fifteen minutes experienced with the inventive process.

The pigment produced according to the inventive process was evaluated in titanium dioxide/polyethylene concentrates, according to the following procedure:

One hundred and nine and one-half (109.5) grams of the pigment was mixed with thirty-six and one-half (36.5) grams of Dow 4012 low density polyethylene (Dow Chemical Company), and 0.05% by weight based on polyethylene of an 80/20 mixture of tris(2,4-di-tertbutylphenyl)phosphite and octadecyl-3-(3,5-di-tertbutyl-4- hydroxyphenyl)propionate, to prepare a 75% by weight titanium dioxide-containing polyethylene concentrate via mastication of the mixture in the mixing bowl of a Plasticorder Model PL-2000 (CW. Brabender Instruments, Inc. South Hackensack, N.J.) at 100 ⁰ C and a mixing speed of 100 rpm. Instantaneous torque and temperature values were then recorded for a nine minute period to ensure equilibrium mixing conditions had been attained. Equilibrium torque values were determined via averaging the measured instantaneous torque values for a two minute period after equilibrium mixing conditions had been achieved. The resulting pigment concentrate was cooled and ground into pellets. The melt flow index value was determined on the resulting pellet concentrate using ASTM method D1238, procedure B. Maximum extruder processing pressure was determined by extruding 100 grams of the 75% concentrate through a 500 mesh screen filter using a 0.75 inch barrel, 25/1 length to diameter extruder attached to the aforementioned Brabender Plasticorder, at an average processing temperature of approximately 19O ⁰ C and at 75 rpm, while recording instrument pressure values at the extruder die. Results from these evaluations are provided in Table 1.

Table 1 Processing Behavior of Titanium Dioxide-Containing Polyethylene Concentrates

In addition to the manufacturing throughput and energy usage advantages detailed above, the hexyltrimethoxysilane- treated titanium dioxide produced according to the process of the instant invention demonstrates utility as an additive in pigmented thermoplastic compositions as indicated by the melt flow index, equilibrium torque, and maximum extruder pressure values observed for the thermoplastic concentrate containing said pigment.

Example 2

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.8% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to about 9.5 and greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63

microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer. The slurry was heated to 6O ⁰ C ₅ acidified to a pH of 2.0 using concentrated sulfuric acid, then treated with 1% alumina, added rapidly as a 357 gram/liter aqueous sodium aluminate solution over a five minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to further digestion for 15 minutes at 60 ⁰ C. After this, adjustment of the pigment slurry pH to a value of 6.2 using 20% by weight aqueous sodium hydroxide solution was followed by digestion for an additional 15 minutes at 6O ⁰ C, with final readjustment of the pH to 6.2, if necessary. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re-dispersed in water with agitation, in the presence of 0.35 % by weight based on pigment of lactic acid as a fluidizing agent, to yield a 60 % solids aqueous titanium dioxide dispersion having a pH of 4.7. The dispersion viscosity was found to be 60 cps, as determined utilizing a Brookfϊeld Viscosimeter (Model DV-I, Spindle #5, 100 rpm).

A 1% aliquot by weight based on pigment of octyltriethoxysilane/tetraethylorthosilicate copolymer (synthesized according to the teachings of Example 1 in U.S. Patent 6,455,158 Bl, yielding a 100 centistoke fluid) was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was then spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. For one thousand grams of pigment, the time required to carry out the spray drying and

simultaneous octyltriethoxysilane/tetraethylorthosilicate copolymer treatment step was fifteen minutes. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the fluidizing agent. As a result, the titanium dioxide dispersion had to be diluted with water to a solids content of less than 40 % in order to lower the viscosity sufficiently to enable pumping to the spray dryer. At 38 % solids, the viscosity of the aqueous titanium dioxide dispersion was found to be 1480 cps, as measured on a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm), with a dispersion pH of 7.8. For one thousand grams of pigment, the time required to carry out the spray drying and simultaneous octyltriethoxysilane/tetraethylorthosilicate copolymer treatment step was forty-five minutes, as opposed to the fifteen minutes experienced with the inventive process.

The pigment produced according to the inventive process was evaluated in titanium dioxide/polyethylene concentrates, according to the procedure described in Example 1. Results from these evaluations are provided in Table 2.

Table 2 Processing Behavior of Titanium Dioxide-Containing Polyethylene Concentrates

In addition to the manufacturing throughput and energy usage advantages detailed above, the octyltriethoxysilane/tetraethylorthosilicate copolymer -treated titanium dioxide produced according to the process of the instant invention further demonstrates utility as an additive in pigmented thermoplastic compositions as indicated by the melt flow index, the equilibrium torque, and the maximum extruder pressure values observed for the thermoplastic concentrate containing said pigment.

Example 3

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.6% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to about 9.5 and above, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63

microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer. The slurry was heated to 5O ⁰ C, acidified to a pH of about 5.0 using concentrated sulfuric acid, then treated with 0.25% zirconia, added rapidly as a 200 gram/liter aqueous zirconium orthosulfate solution, over a five minute period. After the addition of the zirconium orthosulfate, the slurry was maintained at 50 ⁰ C, adjusted to a pH of 8.0 using 20% by weight aqueous sodium hydroxide solution, then treated with 2.8% alumina, added as a 357 gram/liter aqueous sodium aluminate solution over a fifteen minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to an additional 15 minute digestion at 5O ⁰ C, after the completion of the addition of the sodium aluminate solution. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re- dispersed in water with agitation, in the presence of 0.50 % by weight based on pigment, of acetic acid as a fluidizing agent, to yield a 60 % solids aqueous titanium dioxide dispersion having a pH of 4.5. The dispersion viscosity was found to be 50 cps, as determined utilizing a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm).

A 1% aliquot by weight based on pigment of chloropropyltrimethoxysilane was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. For one thousand grams of pigment, the time required to carry out the spray drying and simultaneous chloropropyltrimethoxysilane treatment step was fifteen minutes. The dry

pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the acetic acid fluidizing agent. As a result, the titanium dioxide dispersion had to be diluted with water to a solids content of less than 40 % in order to lower the viscosity sufficiently to enable pumping to the spray dryer. At 38 % solids, the viscosity of the aqueous titanium dioxide dispersion was found to be 900 cps, as measured on a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm), with a dispersion pH of 8.0. For one thousand grams of pigment, the time required to carry out the spray drying and simultaneous chloropropyltrimethoxysilane step was forty minutes, as opposed to the fifteen minutes experienced with the inventive process.

The pigment produced according to the inventive process was evaluated in a water-borne coating, according to the recipe and test procedures below.

Ingredients Parts by Weight

Propylene Glycol 11.9

Tamol® 731 2.4

Igepal® CO-630 1.3

Foammaster® SA-3 0.24

Water 10.2

Titanium dioxide pigment 59.8

The above components were added in the sequence indicated and mixed at 1000 rpm for twenty minutes, after which the components listed below were added in sequence

with continued mixing until homogeneity was achieved, to yield a 22 PVC (pigment volume concentration), 36% NW (percent non-volatiles by volume) water-borne coating with final pH = 8.8 and final viscosity = five poise.

Ingredients Parts by Weight

Rhoplex® AC-2508 ϊ22~5

Foammaster® SA-3 0.20

Ammonium Hydroxide (25%) 0.20

Water 11.2

Texanol® 5.6

Natrosol® 250 MR (added as a 2.5% 10.2 solution containing Proxel® GXL preservative) Lamp black 1.6

Texanol® ester alcohol = 2,2,4-trimethyl-1,3-pentanediol mono (2-methylpropanoate); Eastman

Chemicals Company

Tamol® 731 = diisobutylene/maleic acid alternating copolymer disodium salt 25% in water; Rohm and Haas Company

Igepal® CO-630 = nonylphenoxy poly(ethyleneoxy) ₉ ethanol; Rhodia Inc.

Foammaster® SA-3 = oil-based defoamer; Cognis Corporation

Rhoplex® AC-2508 = aqueous poly(butylacrylate-co-methylmethacrylate) latex dispersion; Rohm and Haas Company

Natrosol® 250 MR = hydroxyethyl cellulose; Hercules Incorporated Aqualon Division

Lamp black = Colortrend® B-Lamp Black; dispersion in mixed glycol solvent; Tenneco

Chemicals, Inc.

Proxel® GXL = 1 ,2-benzoisothiazoiine-3-one; Avecia Inc.

Gloss and tint strength measurements were then performed on the above coating composition according to ASTM method D-523-89 and ASTM method D-2745-00,

respectively, with the results provided in Table 3.

Table 3

Paint Film Properties of Organosilicon Compound-Treated Tiθ ₂ -Containing Water-Bome Paints

In addition to the manufacturing throughput and energy usage advantages detailed above, the chloropropyltrimethoxysilane-treated titanium dioxide produced according to the process of the instant invention thus demonstrates utility as a pigment in a water- borne coating composition, as indicated by the gloss and tint strength values of the paint containing said pigment.

Example 4

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.6% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to about 9.5 and above, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer. The slurry was heated to 50 ⁰ C, acidified to a pH of about 5.0 using concentrated sulfuric acid, then

treated with 0.25% zirconia, added rapidly as a 200 gram/liter aqueous zirconium orthosulfate solution, over a five minute period. After the addition of the zirconium orthosulfate, the slurry was maintained at 5O ⁰ C, adjusted to a pH of 8.0 using 20% by weight aqueous sodium hydroxide solution, then treated with 2.8% alumina, added as a 357 gram/liter aqueous sodium aluminate solution over a fifteen minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to an additional 15 minute digestion at 50 ⁰ C, after the completion of the addition of the sodium aluminate solution. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re- dispersed in water with agitation, in the presence of 0.25% by weight based on pigment, of methanesulfonic acid as a fluidizing agent, to yield a 60 % solids aqueous titanium dioxide dispersion having a pH of 4.5. The dispersion viscosity was found to be 50 cps, as determined utilizing a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm).

A 0.65% aliquot by weight based on pigment of hexyltrimethoxysilane was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 28O ⁰ C, to yield a dry pigment powder. For one thousand grams of pigment, the time required to carry out the spray drying and simultaneous hexyltrimethoxysilane treatment step was fifteen minutes. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam

injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the methanesulfonic acid fluidizing agent. As a result, the titanium dioxide dispersion had to be diluted with water to a solids content of less than 40 % in order to lower the viscosity sufficiently to enable pumping to the spray dryer. At 38 % solids, the viscosity of the aqueous titanium dioxide dispersion was found to be 900 cps, as measured on a Brookfield Viscosimeter (Model DV-I, Spindle #5, 100 rpm), with a dispersion pH of 8.0. For one thousand grams of pigment, the time required to carry out the spray drying and simultaneous hexyltrimethoxysilane step was forty minutes, as opposed to the fifteen minutes experienced with the inventive process.

The resulting pigment produced according to the inventive process was evaluated in a water-borne coating, according to the recipe and test procedures described in Example 3. Results are provided in Table 4.

Table 4

Paint Film Properties of Organosilicon Compound-Treated Tiθ ₂ -Containing Water-Borne Paints

In addition to the manufacturing throughput and energy usage advantages detailed above, the hexyltrimethoxysilane-treated titanium dioxide produced according to the process of the instant invention demonstrates utility as a pigment in a water-borne coating

composition, as indicated by the gloss and tint strength of the paint containing said pigment.

Example 5

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride containing 1.0% alumina was dispersed in water in the presence of 0.15% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to 9.5 and greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer (Microtrac Inc. Montgomeryville, PA).

The resulting slurry, diluted to 30% solids by weight, was heated to 9O ⁰ C then treated with 3.0%, calculated as silica by weight of final pigment, of sodium silicate, added over 20 minutes as a 250 gram/liter aqueous sodium silicate solution (SiO ₂ Na ₂ O = 3.5). While maintaining the temperature at 9O ⁰ C, the pH of the slurry was slowly decreased to pH = 5.0 using 25% by weight aqueous sulfuric acid solution, over a 55 minute period. Following a digestion period of 15 minutes, 2.0% alumina, by weight of final pigment, was added over 15 minutes as a 357 gram/liter aqueous sodium aluminate solution while maintaining the pH of the slurry between a value of 8.0 and 8.5 via the concomitant addition of 25% aqueous sulfuric acid.

The dispersion was allowed to equilibrate at 90 ⁰ C for 15 minutes, at which point the pH of the slurry was re-adjusted to 5.8, prior to filtration while hot. The resulting

filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre- adjusted to a pH of 7.0, equal to the weight of recovered pigment.

The washed semi-solid filtrate was subsequently re-dispersed in water with agitation in the presence of 0.50%, by weight based on pigment, of hexyltrimethoxysilane. The resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer (Invensys APV Silkeborg, Denmark), maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane, utilizing a steam to pigment weight ratio of 2.5, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the hexyltrimethoxysilane. The resulting pigment produced according to the inventive process and the comparative pigment were both evaluated for paint film gloss and tint strength performance in a water-borne coating, according to the recipe and test procedures used in Examples 3 and 4. Results are provided in Table 5.

Table 5

Paint Film Properties of Organosilicon Compound-Treated Tiθ ₂ -Containing Water-Borne Paints

The aqueous coating composition produced according to the instant invention,

comprising a titanium dioxide pigment having deposited thereon an inorganic oxide surface treatment of 3.0% silica and 2.0% alumina, both by weight of the pigment, and an organic surface treatment comprising 0.50% by weight of pigment of hexyltrimethoxysilane according to the present invention, thus demonstrates improved properties as indicated by the increased gloss and tint strength values for the inventive coating composition versus the comparative example.

Example 6

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride containing 1.0% alumina was dispersed in water in the presence of 0.15% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to a value of 9.5 and greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer.

The resulting slurry, diluted to 30% solids by weight, was heated to 90°C then treated with 3.0%, calculated as silica by weight of final pigment, of sodium silicate, added over 20 minutes as a 250 gram/liter aqueous sodium silicate solution (SiO ₂ INa ₂ O = 3.5). While maintaining the temperature at 9O ⁰ C, the pH of the slurry was slowly decreased to pH = 5.0 using 25% by weight aqueous sulfuric acid solution, over a 55 minute period. Following a digestion period of 15 minutes, 2.0% alumina, by weight of final pigment, was added over 15 minutes as a 357 gram/liter aqueous sodium aluminate

solution while maintaining the pH of the slurry between a value of 8.0 and 8.5 via the concomitant addition of 25% aqueous sulfuric acid.

The dispersion was allowed to equilibrate at 90 ⁰ C for 15 minutes, at which point the pH of the slurry was re-adjusted to 5.8, prior to filtration while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre- adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed semi-solid filtrate was subsequently re-dispersed in water with agitation in the presence of 1.0%, by weight based on pigment, of propyltrimethoxysilane according to the present invention. The resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane, utilizing a steam to pigment weight ratio of 2.5, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the propyltrimethoxysilane. The resulting pigment produced according to the inventive process and the comparative pigment were both evaluated for paint film gloss and tint strength performance in a water-borne coating, according to the recipe and test procedures described in Examples 3 through 5. Results are provided in Table 6.

Table 6

Paint Film Properties of Organosilicon Compound-Treated Tiθ ₂ -Containing Water-Bome Paints

The coating composition produced according to the instant invention, comprising a titanium dioxide pigment having deposited thereon an inorganic oxide surface treatment of 3.0% silica and 2.0% alumina, both by weight of the pigment, and an organic surface treatment comprising 1.0% by weight of pigment of propyltrimethoxysilane, further demonstrates improved properties as indicated by the increased gloss and tint strength values for the inventive coating composition versus the comparative example.

Example 7

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride containing 1.0% alumina was dispersed in water in the presence of 0.15% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to a value of 9.5 and greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer.

The resulting slurry, diluted to 30% solids by weight, was heated to 90 ⁰ C then

treated with 3.0%, calculated as silica by weight of final pigment, of sodium silicate, added over 20 minutes as a 250 gram/liter aqueous sodium silicate solution (SiO ₂ )Na ₂ O = 3.5). While maintaining the temperature at 90 ⁰ C, the pH of the slurry was slowly decreased to pH = 5.0 using 25% by weight aqueous sulfuric acid solution, over a 55 minute period. Following a digestion period of 15 minutes, 2.0% alumina, by weight of final pigment, was added over 15 minutes as a 357 gram/liter aqueous sodium aluminate solution while maintaining the pH of the slurry between a value of 8.0 and 8.5 via the concomitant addition of 25% aqueous sulfuric acid.

The dispersion was allowed to equilibrate at 9O ⁰ C for 15 minutes, at which point the pH of the slurry was re-adjusted to 5.8, prior to filtration while hot The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre- adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed semi-solid filtrate was subsequently re-dispersed in water with agitation in the presence of 1.0%, by weight based on pigment, of 3-chloropropyltrimethoxysilane according to the present invention. The resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane, utilizing a steam to pigment weight ratio of 2.5, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the chloropropyltrimethoxysilane. The resulting pigment produced according to the inventive process and the comparative pigment were both

evaluated for paint film gloss and tint strength performance in a water-borne coating, according to the recipe and test procedures of previous examples. Results are provided in Table 7.

Table 7

Paint Film Properties of Organosilicon Compound-Treated Tiθ ₂ -Containing Water-Borne Paints

The coating composition produced according to the instant invention, comprising a titanium dioxide pigment having deposited thereon an inorganic oxide surface treatment of 3.0% silica and 2.0% alumina, both by weight of the pigment, and an organic surface treatment comprising 1.0% by weight of pigment of chloropropyltrimethoxysilane, further demonstrates improved properties as indicated by the increased gloss and tint strength values for the inventive coating composition versus the comparative example.

Example 8

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.6% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to a value of 9.5 or greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller

than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer. The slurry was heated to 50 ⁰ C, acidified to a pH of about 5.0 using concentrated sulfuric acid, then treated with 0.25% zirconia, added rapidly as a 200 gram/liter aqueous zirconium orthosulfate solution, over a five minute period. After the addition of the zirconium orthosulfate, the slurry was maintained at 50 ⁰ C, adjusted to a pH of 8.0 using 20% by weight aqueous sodium hydroxide solution, then treated with 2.8% alumina, added as a 357 gram/liter aqueous sodium aluminate solution over a fifteen minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to an additional 15 minute digestion at 50 ⁰ C, after the completion of the addition of the sodium aluminate solution. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 6O ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re- dispersed in water with agitation. A 1.0% aliquot, by weight based on pigment, of chloropropyltrimethoxysilane was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the chloropropyltrimethoxysilane. The resulting pigment

produced according to the inventive process and the comparative pigment sample were both evaluated in a water-borne coating, according to the recipe and test procedures described in previous examples. Results are provided in Table 8.

Table 8

Paint Film Properties of Organosilicon Compound-Treated TiCVContaining Water-Borne Paints

The coating composition produced according to the instant invention, comprising a titanium dioxide pigment having deposited thereon an inorganic oxide surface treatment of 0.25% zirconia and 2.8% alumina, both by weight of the pigment, and an organic surface treatment comprising 1.0% by weight of pigment of chloropropyltrimethoxysilane according to the present invention, further demonstrates improved properties as indicated by the increased gloss and tint strength values for the inventive coating composition versus the comparative example.

Example 9

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.6% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to a value of 9.5 and greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume

average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer. The slurry was heated to 50 ⁰ C, acidified to a pH of about 5.0 using concentrated sulfuric acid, then treated with 0.25% zirconia, added rapidly as a 200 gram/liter aqueous zirconium orthosulfate solution, over a five minute period. After the addition of the zirconium orthosulfate, the slurry was maintained at 50 ⁰ C, adjusted to a pH of 8.0 using 20% by weight aqueous sodium hydroxide solution, then treated with 2.8% alumina, added as a 357 gram/liter aqueous sodium aluminate solution over a fifteen minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to an additional 15 minute digestion at 5O ⁰ C, after the completion of the addition of the sodium aluminate solution. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re- dispersed in water with agitation, in the presence of 0.25% by weight based on pigment, of methanesulfonic acid as a fluidizing agent. A 0.65% aliquot, by weight based on pigment, of hexyltrimethoxysilane was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the hexyltrimethoxysilane. The resulting pigment produced according to the inventive process and the comparative pigment sample were both evaluated in a water-borne coating, according to the recipe and test procedures described in previous examples. Results are provided in Table 9.

Table 9

Paint Film Properties of Organosilicon Compound-Treated Tiθ ₂ -Containing Water-Borne Paints

The coating composition produced according to the instant invention, comprising a titanium dioxide pigment having deposited thereon an inorganic oxide surface treatment of 0.25% zirconia and 2.8% alumina, both by weight of the pigment, and an organic surface treatment comprising 0.65% by weight of pigment of hexyltrimethoxysilane, further demonstrates improved properties as indicated by the increased tint strength value for the inventive coating composition versus the comparative example.

Example 10

Particulate titanium dioxide pigment intermediate obtained from the vapor phase oxidation of titanium tetrachloride and containing 0.6% alumina in its crystalline lattice was dispersed in water in the presence of 0.18% by weight (based on pigment) of sodium hexametaphosphate dispersant, along with a sufficient amount of sodium hydroxide to adjust the pH of the dispersion to a value of 9.5 and greater, to achieve an aqueous dispersion with a solids content of 35% by weight. The resulting titanium dioxide slurry

was sand milled, using a zircon sand-to-pigment weight ratio of 4 to 1, until a volume average particle size was achieved wherein more than 90% of the particles were smaller than 0.63 microns, as determined utilizing a Microtrac XlOO Particle Size Analyzer. The slurry was heated to 50 ⁰ C, acidified to a pH of about 5.0 using concentrated sulfuric acid, then treated with 0.25% zirconia, added rapidly as a 200 gram/liter aqueous zirconium orthosulfate solution, over a five minute period. After the addition of the zirconium orthosulfate, the slurry was maintained at 5O ⁰ C, adjusted to a pH of 8.0 using 20% by weight aqueous sodium hydroxide solution, then treated with 2.8% alumina, added as a 357 gram/liter aqueous sodium aluminate solution over a fifteen minute period. During the addition of the sodium aluminate solution, the pH of the slurry was maintained between a value of 8.0 and 8.5 via the addition of sulfuric acid, prior to an additional 15 minute digestion at 50 ⁰ C, after the completion of the addition of the sodium aluminate solution. The dispersion was then filtered while hot. The resulting filtrate was washed with an amount of water, which had been preheated to 60 ⁰ C and pre-adjusted to a pH of 7.0, equal to the weight of recovered pigment. The washed filtrate was subsequently re- dispersed in water with agitation. A 0.65% aliquot, by weight based on pigment, of hexyltrimethoxysilane was added to the resulting titanium dioxide dispersion with mixing, and the resulting pigment dispersion was spray dried using an APV Nordic PSD52 Spray Dryer, maintaining a dryer inlet temperature of approximately 280 ⁰ C, to yield a dry pigment powder. The dry pigment powder was then steam micronized in the presence of 0.35% by weight based on pigment of trimethylol propane utilizing a steam to pigment weight ratio of five, with a steam injector pressure set at 146 psi and micronizer ring pressure set at 118 psi, completing the finished pigment preparation.

As a comparative example, the same procedure described above was repeated, but in the absence of the addition of the hexyltrimethoxysilane. The resulting pigment produced according to the inventive process and the comparative pigment sample were both evaluated in a water-borne coating, according to the recipe and test procedures described in previous examples. Results are provided in Table 10.

Table 10

Paint Film Properties of Organosilicon Compound-Treated TiCVContaining Water-Borne Paints

The coating composition produced according to the instant invention, comprising a titanium dioxide pigment having deposited thereon an inorganic oxide surface treatment of 0.25% zirconia and 2.8% alumina, both by weight of the pigment, and an organic surface treatment comprising 1.0% by weight of pigment of hexyltrimethoxysilane, still further demonstrates improved properties as indicated by the increased gloss value for the inventive coating composition versus the comparative example.