IMPROVEMENT IN BULKING PIGMENTS

Abstract: A highly bulked kaolin pigment is prepared by mixing a small but effective amount of water-soluble cationic polyelectrolyte flocculant with a kaolin clay pigment in the presence of water to prepare a bulked clay pigment product. Upon dewatering, the resultant polyelectrolyte treated clay product can be dispersed to form high solids clay-water slurries useful in making aqueous coating colors suitable for manufacturing coating lightweight publication papers or the pigment can be used as a filler for paper webs. Slurries having stable viscosity at elevated temperature are prepared by using as the dispersant a combination of a polyacrylate salt and a nonionic surfactant.

Description: This invention relates to improving the stability of slurries of bulking kaolin clay pigments when the slurries are exposed to elevated temperatures, for example when the slurries are prepared into coating colors in a steam jet cooker or shipped and stored under high ambient temperatures. Finely divided refined kaolin clay is widely used as a pigment to provide a glossy, white opaque surface finish on printing paper. The clay is applied as an aqueous "coating color" which comprises a clay pigment, a dispersing agent for the clay, a suitable adhesive such as a polymer latex, starch, or mixtures thereof and other minor additives. Present-day coatings are applied at high machine speeds which necessitate the use of high solids coating colors. The formulation of coating colors at high solids requires the initial provision of fluid high solids clay-water suspensions or "slips". These suspensions are subsequently mixed with adhesive dispersions or suspensions to prepare the coating colors. High solids clay-water suspensions of hydrous (uncalcined) clays generally contain in excess of 65% clay solids (65 parts by weight dry clay to 35 parts by weight water). Typically, solids are about 70%. A dispersing (deflocculating) agent, conventionally a sodium condensed phosphate salt, or sodium polyacrylate, is present in the high solids suspensions in order to impart fluidity, since the systems do not flow in the absence of the dispersing agent. Kaolin clay pigments must meet certain requirements with regard to rheological properties and to the properties of the coated sheet material. The visosity of the high solids suspension of the clay coating pigment must be sufficiently low to permit mixing and pumping. After the adhesive is incorporated, the resulting coating color must also have suitable viscosity for handling and application to the paper sheet. In addition, it is highly desirable to obtain a coated calendered sheet which has good opacity, gloss, brightness and printability. It is the conventional practice in the art to improve the opacifying or hiding power of coating colors by blending the clay pigments with more costly pigments having greater opacifying power, such as TiO₂. The industry has long sought a kaolin clay pigment which imparts improved opacifying power to coated paper without sacrificing gloss and printability and which can preferably be used in the absence of other more expensive pigments. High bulking clay pigments offer the opportunity of maintaining or improving the opacity, gloss and printability of coated paper incorporated at lower coating weights, thereby reducing the pigment cost for coating colors. Bulking pigments are those which provide coatings having high opacification at a low coat weight. Generally, bulking is achieved by introducing voids in a pigment structure which contribute to increase light scatter. Controlled calcination of kaolin clays results in one type of bulking clay pigment. U. S. Patent Nos. 4,075,030; U. S. 4,076,548 and U.S. 4,078,941 teach increasing the opacifying power of hydrous kaolin clays by "selectively flocculating" ultrafine clay particles with a low molecular weight polyamine flocculating agent (e.g. ethylene diamine or hexamethylene diamine) or with long carbon chain amines or certain quaternary ammonium salts (e.g., "ditallowdimethyl" ammonium chloride) in the presence of a mineral acid flocculating agent, e.g., sulfuric acid, and optionally with the added presence of citric acid or mica or both. The selective flocculating treatment allegedly incorporates voids in the clay to form a low density, high bulking pigment which when used as a coating color pigment improves the opacity of paper coated therewith. These patents do not disclose the use of polymers nor do they contain information regarding the ability to disperse the bulked clay to prepare clay-slurries having acceptable rheological characteristics for commercial use. We are aware of the fact that efforts to exploit bulking pigments to the paper industry have been thwarted among other things by the poor rheology of the pigments. Generally, paper makers seek to use clay coating pigments capable of forming high solids clay-water slurries which have a low shear viscosity below 1000 cp, preferably below 500 cp when measured by the Brookfield viscometer at 20 rpm. High shear viscosity for these slurries should be such that they are no more viscous than a slurry having a Hercules endpoint viscosity of 500 rpm, preferably 800 rpm, using the "A" bob at 16 X 10⁵ dyne-cm. Those skilled in the art are aware that when using the Hercules viscometer and measuring endpoints of 1100 rpm or higher, endpoint viscosities are reported in units of dyne-cm at 1100 rpm; apparent viscosity increases as the value for dyne-cm increases. It is conventional to use the abbreviated term "dyne". Thus, a "2 dyne" clay slurry is less viscous than a "9 dyne clay" slurry. As used hereinafter the expressions 500 rpm or higher, or 800 rpm or higher, are intended to include lower viscosities such that endpoint measurements are at 1100 rpm and the values are reported as dynes. For reasons of economy, the manufacture of refined kaolin pigments usually necessitates sizing and purifying crude clay while the clay is in the form of a fluid deflocculated aqueous slurry, bleaching the clay while in a flocculated state, filtering the flocculated clay to remove liquid water and then dispersing the flocculated clay to form a high solids slurry that is sold as such or is dried, usually in a spray dryer, to provide a dry refined pigment capable of being mixed with water to form a dispersed fluid suspension. The latter form of clay is frequently referred to as a "predispersed" grade of clay even though the clay is dry and is not present in dispersed state until it is mixed with water. Another problem encountered in the manufacture of bulking pigments from clay is to produce a bulked structure that is sufficiently durable to survive during various stages of production and end-use but is also capable of being dispersed to form high solids clay-water slurries having acceptable rheology. When the general wet processing scheme described above is employed to make bulked structures by adding a bulking agent before filtration, the bulked structure must still be present in the filter cake containing the bulked assemblages when the filter cake is "made down" into a fluid slurry. The expressions "make down" and "made down" are conventional in the industry and refer to the preparation of dispersed pigment-water slurries. In some cases, it may be necessary to apply mechanical work to the filter cake to reduce the low shear viscosity to usable values. The bulked structure must be sufficiently tenacious to survive the mechanical forces during such treatment. Bulking pigments must also be sufficiently stable under the influence of shear to maintain the bulked structure under the high shear rates encountered in pumping high solids clay water slurries. Moreover, a bulked structure must be capable of being retained when the deflocculated clay water slurry is formed into a coating color using standard makedown equipment. Also, the bulked structure must survive during the coating application and subsequent calendering. The fragility of the bulked structures obtained by chemical treatments of hydrous clays has limited their commercial use. Commercial bulking clays heretofore used by the paper industry are prepared by calcining fine particle size hydrous clays. In such case, calcination "sets" the bulked structure such that it is sufficiently durable to survive during manufacturing handling and use. Generally, a criterion for durability of a bulked structure is the retention of improved opacification (light scattering). It is possible to use water-soluble cationic polyelectrolytes to produce bulked hydrous clay pigments having a combination of desirable properties. These cationic polyelectrolytes are high charge density materials and have the ability to flocculate clay-water slurries. Cationic polyelectrolyte flocculants have been used in the past to clarify various suspensions such as river waters containing suspended fine solids, municipal waste and sewage sludge. The efficiency of such flocculants is frequently evaluated by measuring the ability of the flocculant to clarify clay suspensions. It is also known that various polymers including certain cationic polyelectrolytes will increase the rate at which suspensions of clay filter. However, the use of polymeric filter aids to increase filtration may adversely affect the rheology of kaolin clay intended for use as high performance pigment in the paper industry. Furthermore, filter cake solids are usually decreased when polymers are used as filter aids. As a result drying costs are increased. This may reduce the economic benefit of increased filtration rates. To the best of our knowledge, the quality segment of the clay industry devoted to producing high performance pigments and fillers does not utilize polymeric filter aids to produce clay pigments. EP Patent Application 86305151.2 (EP-A-0245553) provides new relatively inexpensive kaolin pigments with a stable bulked structure but also capable of being mixed with water to form clay-water slurries and coating colors having useable low and high shear viscosity. The new bulked pigments, obtained using cationic polyelectrolytes to bulk the clay, can he applied to paper at low coat weights. Coated printing paper possessing superior printability, especially by rotogravure and offset methods is obtained. However, slurries of the bulked pigment tend to increase in viscosity when exposed to high temperature, for example when prepared into starch coating colors by the known steam jet cooking procedure. Similarly, viscosity may increase slowly upon exposure to elevated storage temperature (e.g. 100°F), over a period of several weeks. The present invention provides slurries of bulked kaolin pigments which have improved stability at elevated temperatures. In accordance with the present invention slurries of bulked kaolin pigments are dispersed with a combination of nonionic surfactant and polyacrylate salt dispersant, such as, for example, sodium polyacrylate. The nonionic surfactants used in practice of the invention are compatible with water and oil and have an HLB value of 3 to 18, e.g. 5 to 14. Suitable nonionic surfactants fitting this description are well known to those skilled in the pigments, fillers (extenders) and coatings arts. Nonionic surfactants useful in this invention include the nonylphenoxypoly(ethyleneoxy) ethanols having the average formula: wherein n is a number of 4 to 12, preferably 7 to 9, and the compound has an HLB value of 3 to 18, preferably 5 to 14. Specific surfactants of this type are the Igepals made and sold by GAF Corp. of Charlotte, North Carolina, including Igepal 610 having formula I (in which n has an average value of about 7.82) and an HLB of 12.2; Igepal CO-210 having formula I (wherein n, has an average value of about 1.33) and an HLB of 4,6; Igepal CO-520 having formula I (wherein n has an average value of about 5.4) and an HLB of 10.0; Igepal CO-720 having formula I (wherein n has an average value of about 12.9) and an HLB of 14.2; and the like. Other nonionic surfactants useful in this invention are the condensates of ethylene oxide with hydrophobic condensates formed by condensing propylene oxide and propylene glycol. This type of nonionic surfactant can be depicted by the average formula: HO(C₂H₄O) x (C₃H₆O) y (C₂H₄O) z H (II) in which x, y and z are numbers of such relative values as to provide an HLB value of 3 to 18, preferably 5 to 14. Specific surfactants of this type include the Pluronics sold by BASF Wyandotte Industrial Chemical Group, specifically Pluronic L-72 having an HLB of 6.5, Pluronic L-31 having an HLB of 4.5, Pluronic L-64 having an HLB of 15, and the like. The Pluronics, however, may present an odor problem when clay products containing them are spray dried or when they are otherwise subjected to elevated temperatures and thus they are less preferred than the Igepals such as Igepal 610. The preferred surfactant is of the decyloxy poly (ethyleneoxy) ethanol type having the average formula C₁₀H₂₁O(C₂H₄O) n CH₂CH₂OH, where n can range from 6 to 8. The HLB is preferably 12-14. This type of surfactant provided best viscosity stability at elevated temperatures. The slurry according to the invention preferably contains up to 0.3% (e.g. up to 0.15%) of nonionic surfactant based on the weight of clay. The proportion of nonionic surfactant in the novel mixture of bulked clay, polyacrylate salt such as sodium polyacrylate, and surfactant is not narrowly critical and can be e.g. from 0.05% to 0.25% on a dry clay basis, preferably 0.1% to 0.15%. The amount of polyacrylate can be e.g. from 0.05% to 0.3% on a dry clay basis, preferably 0.1% to 0.175%. Other examples of nonionic surfactants having an appropriate HLB value falling within the above-described ranges can be found by reference to standard publications such as McCutcheon's 1982: Combined Edition, published by McCutcheon's Division MC Publishing Company, 175 Rock Road, Glen Rock, New Jersey 07452, or earlier editions such as McCutcheon's: Detergents and Emulsifiers, published by Allured Publishing Company, Ridgewood, New Jersey, 1974. In addition, trade publications such as "Technical Data on Pluronic Polyols", OS 796, published by BASF Wyandotte Corporation, Organic Specialties & Fine Chemicals Dept., Parsippany, New Jersey 07054, or "Igepal CA Nonionic Surfactants, a Homologous Series of Octylphenoxy Poly (ethyleneoxy) Ethanols" #2303-020, published by GAF Corporation, 1361 Alps Road, Wayne New Jersey 07470, can be consulted for further examples of nonionic surfactants usable in this invention. The bulked kaolin clays used in the novel mixtures of this invention are preferably those bulked by addition of cationic polyelectrolytes as described in EP Application 86305151.2. Preparation of Preferred Bulked Pigments (EP 86305151.2 ) It has been determined that the shape of the particle size distribution curve of the kaolin clay used to produce pigments of the invention has an effect on the ultimate coating properties of the polyelectrolyte treated kaolin clay mineral. Thus, a clay having the following particle size distribution characteristics has been found to provide optimum rheology and coating properties: a median particle size of 0.55 micrometers and a particle size distribution such that 88 ± 2% of the particles have an equivalent spherical diameter less than 2 micrometers and not more than 25% by weight, preferably rot more than 20% by weight, have an equivalent spherical diameter less than 0.3 micrometers. If the particle size is too coarse, gloss and opacity suffer although opacity will be greater than the clay before treatment with polyelectrolyte. If the quantity of ultrafine particles, i. e., particles 0.3 micrometers and finer, is too great, the rheology of the pigment may be such that it has limited, if any, use. In order to achieve the desired particle size distribution of the kaolin that is eventually formed into a bulked structure, it is generally necessary to perform one or more particle size separations on the crude clay. Generally, such processing includes degritting, followed by differential gravitational or centrifugal sedimentation to recover a size fraction of desired particle size, such as for example, a fraction that is 90% by weight finer than 2 micrometers and does not contain an excessive amount of ultrafine particles. The content of ultrafines and median (weight) particle size of such fraction will vary, depending on the particle size distribution of the crude clay. In order to perform these operations successfully, it is essential that the clay be present in the form of discrete particles in water rather than flocs so that the particles can be accurately separated into different size ranges. The clay is therefore preferably treated with a deflocculant (dispersing agent) which will give all the particles a negative electric charge, and cause them to repel each other when the particles are suspended in water. The clay dispersant used at this stage is generally referred to as a "primary" dispersant. Dispersants used to deflocculate suspensions of previously processed clay (such as dispersants added to filter cakes) are termed "secondary" dispersants or deflocculants. Suitable dispersing agents used for primary dispersion in practice of the present are conventional and include water soluble salts of a condensed phosphate, such as a pyrophosphate, e.g., tetrasodium pyrophosphate, (TSPP), a water soluble salt of a polysilicic acid, for example, sodium silicate, or a water soluble organic polymeric dispersing agent, for example a polyacrylate or a polymethylmethacrylate salt having a molecular weight of 500 to 10,000. The amount of dispersing agent used will generally be from about 0.025 to 0.2% by weight based on the weight of the dry clay. Generally, particle size separations are performed using deflocculated aqueous suspensions having a solids content of 20-40% by weight. Other solids levels may be used to carry out such separations. The median particle size of the clay particles that are treated with the cationic polyelectrolyte may, eg range from 0.4 to 0.7 micrometers, equivalent spherical diameter (e.s.d.), preferably 0.5 to 0.6 micrometers, as determined by conventional sedimentation techniques using the SEDIGRAPH® particle size analyzer, supplied by Micromeretics, Inc. From 80% to 95% by weight of the particles are preferably finer than 2 micrometers, e.s.d. The content of fines below 0.3 micrometer e.s.d. preferably below 35 weight percent, more preferably below 25 weight %, and most preferably 20 weight percent or below. It should be understood that the measurements of the size of clay particles that are 0.3 micrometer or finer are of limited reproducibility. Thus, when a SEDIGRAPH analyzer is employed, the value for weight percent may be ± 5% when tested by another operator or a different SEDIGRAPH analyzer is employed. Most preferably, median particle size is 0.6 ± 0.05 micrometers, e.s.d., with 85 to 90% by weight of the particles finer than 2 micrometers, e.s.d., and less than 20% by weight or less finer than 0.30 micrometers, e.s.d. Present experience indicates that when the clay to which polyelectrolyte is added contains an excessive amount of ultrafine particles (particles 0.3 micrometers or finer), the Brookfield viscosity may be higher than and Hercules viscosity lower than bulked pigments obtained from clays with a smaller amount of ultrafine particle. One trial resulted in a failure because of excessively high low shear viscosity of the product when the feed clay contained more than the desired amount of particles finer than 0.3 micrometers. Blending of clay fractions may be advantageous or necessary with some crudes to provide a clay feed having a desirable particle size distribution. The amount of polyelectrolyte employed is carefully controlled to be sufficient to improve the opacity of the clay as a result of forming a bulked (aggregated) structure in which the aggregates are sufficiently strong to survive mechanical forces exerted during manufacture and end use but is carefully limited so as to assure that the product can be formed into a clay-water slurry that has a solids content of 60% or higher, which slurry has acceptable rheology. The amount of the cationic polyelectrolyte salt used to treat the kaolin clay may vary with characteristics of the polyelectrolyte including charge density of the polyelectrolyte, the particle size distribution of the clay and solids content of the clay slurry to which the polyelectrolyte is added. Using the presently preferred dimethyldiallyl ammonium salt polyelectrolyte with clay having a median size in the range of about 0.5 to 0.6 micrometers, and having less than 20% finer than 0.3 micrometers and adding polyelectrolyte to a previously deflocculated clay-water suspension having a clay solids content of 20-40% by weight, useful amounts range from 0.03 to 0.15% by weight of the moisture free weight of the clay, most preferably 0.07 to 0.1% by weight. When insufficient polyelectrolyte is used, the effect on opacity and printability in coating applications may be less than desired. On the other hand, an excessive amount of the polyelectrolyte may impair other desired properties of the clay, especially rheology. The polyelectrolyte, which is water soluble, can be added to the slurry as a dilute aqueous solution, e. g. 1/4-2% concentration on a weight basis, with agitation to achieve good distribution in the slurry. Ambient temperature can be used. It may be advantageous to heat the slurry of clay, solution of polyelectrolyte, or both to 150° to 180°F. The cationic polyelectrolyte flocculants that are used have closely spaced charged centers and therefore are high charge density materials. Because of this, the reaction with the clay mineral is extremely rapid and appears to be complete in a relatively short time. While we do not wish to be limited by any particulars of the reaction mechanisms, we believe that the clay mineral cations such as H⁺, Na⁺, and Ca⁺⁺ are replaced with the positively charged polymeric portion of the cationic polyelectrolyte at the original mineral cation location and that this replacement reduces the negative charge on the clay particles which in turn leads to coalescence by mutual attraction. Charge centers near the end of the polymer chain react and bridge with neighboring particles until the accessible clay cation exchange centers or the polymer charge centers are exhausted. The bridging strengthens the bond between the particles, thereby providing a highly shear resistant, bulked clay mineral composition. The presence of chloride ions in the filtrate in the case of dimethyldiallyl ammonium chloride may be an indication that at least one stage of the reaction between clay particles and quaternary salt polymer occurs by an ion-exchange mechanism. The amount of polyelectrolyte added is less than that calculated to provide a monolayer on the surface of clay particles. Water soluble cationic polyelectrolyte flocculants are well known in the art and many are known to increase the rate at which clay slurries filter - see, for example, U. S. 4,174,279. Cationic polyelectrolyte flocculants are characterized by a high density of positive charge. (Positive charge density is calculated by dividing the total number of positive charges per molecule by the molecular weight). Generally the high charge density of polyelectrolyte flocculants exceeds 1 X 10⁻³ and such materials do not contain negative groups such as carboxyl or carbonyl groups In addition to the alkyldiallyl quaternary ammonium salts, other quaternary ammonium cationic flocculants are obtained by copolymerizing aliphatic secondary amines with epichlorohydrin. See U.S. 4,174,279. Still other water-soluble cationic polyelectrolytes are poly (quaternary ammonium) polyether salts that contain quaternary nitrogen in a polymeric backbone and are chain extended by ether groups. They are prepared from water-soluble poly (quaternary ammonium salts) containing pendant hydroxyl groups and bifunctionally reactive chain extending agents; such polyelectrolytes are prepared by treating N, N, N (1) , N (1) tetraalkyl-hydroxyalkylenediamine and organic dihalide such as dihydroalkane or dihaloether with epoxy haloalkane. Such polyelectrolytes and their use in flocculating clay are disclosed in U.S. 3,663,461. Other water-soluble cationic polyelectrolyte flocculants are polyamines. Polyamine flocculants are usually supplied commercially under trade designations and chemical structure and molecular weight are not provided by the suppliers. A dimethyl diallyl quaternary ammonium chloride polymer commercially available under the trademark designation Polymer 261 LV from the Calgon Corporation having a molecular weight estimated to be 50,000 - 250,000 has been found particularly useful in the practice of the present invention and has FDA approval (Code 176-170) for use in paper and board that comes in contact with aqueous and fatty foods. Many reagents heretofore proposed to bulk clay do not have FDA approval. However, the invention is not limited to Polymer 261 LV since other cationic flocculants appear to provide equivalent, if not superior results. Limited experimental work with kaolin clay that produced desired results using 0.08% Calgon 261 LV polymer (dimethyl dially ammonium chloride, said by the supplier to have a molecular weight between 50,000 and 250,000) indicates that similar results would be expected with water-soluble cationic flocculants supplied with the following trademarks when used in the quantities indicted (100% active weight basis): NALCOLYTE® 7107 (0.25%), NALCLEAR® 7122 (1.00%), NALCOLYTE® 8102, (0.50%), NALCOLYTE® 8101 (1.0%), NALCOLYTE® 8100 (1.0%). Information from the suppliers indicates that these polyelectrolytes are: NALCLEAR 7122-water/oil emulsion of aminomethylated polyacrylamide quaternary, low molecular weight. NALCOLYTE 8101-Aqueous solution of polyquaternaryamine chloride moderate molecular weight. NACOLYTE 7107-aqueous solution of polyamine, low molecular weight. NALCOLYTE 8100-aqueous solution of quaternary polyamine, moderate molecular weight. The exact structural formula of the preferred diallyl polymers has not been completely delineated. It is believed that either of the two ring structures set forth below could represent the structure. wherein: R and R₁ are selected from hydrogen and alkyl groups of 1 to 18 carbon atoms, n indicates repeating units, and A⁻ is an anion such as Cl⁻. The preferred compounds are dialkyl diallyl quaternary ammonium salt polymers which contain alkyl groups R and R₁ of 1 to 4 carbon atoms, preferably methyl, and n is an integer of 5 to 1000. Such polyelectrolytes are known flocculating agents. For example, U. S. 3,994, 806 and U. S. 4,450,092 disclose the use of dimethyl diallyl ammonium chloride salt polymers in combination with aluminum and iron salts or a polyacrylamide in coagulating finely divided solids in turbid waters. It should be understood that incorporation of other anions in place of chloride ion is possible, although performance could be affected. Examples of such other anions are acetate, sulfate, nitrate and hydroxide. Satisfactory results have been realized when the polyelectrolyte was added to deflocculated clay suspensions having pH values in the range of 6 to 9. After addition of polyelectrolyte, the suspension is substantially thickened is a result of flocculation. The resulting thickened system can then be acidified, typically to a pH below 5, usually pH 3-4, and bleached using a conventional clay bleach (hydrosulfite salt such as sodium hydrosulfite) and then at least partially dewatered to remove free water and place the recovered bulked clay in a form such that it can be washed to remove ions in th flocculated clay suspension. Normally dewatering is carried out on a filter, for example a rotary vacuum filter. Bleaches are usually reductants which reduce any color forming ferric Iron (Fe³⁺) constituents to a more water soluble and therefore more easily removeable ferrous state (Fe²⁺). Suitable bleaching agents include water soluble hydrosulfite salts, and borohydride salts which are advantageously added to the clay mineral slurry in an amount of from 1 to 15 lb., most preferably about 2 to 6 lbs., of bleaching agent per ton of dry clay (the tons referred to herein being short tons). The slurry of polymer treated clay is acidified before filtration in order to enhance filtration even if bleaching is not carried out. The clay suspension may be dewatered by filtering to a moist filter cake having a solids content of 50 to 60% by weight. The filter cake can then be washed to remove soluble material & then fluidized by the addition of a secondary dispersing agent, such as tetrasodium pyrophosphate to the filter cake, suitably at a concentration of 0.01 to 1.0 percent by weight based on the dry clay solids and preferably 0.05 to 0.15 percent by weight. Polyacrylate salts are preferably used to fluidize the filtercake although mixtures thereof with condensed phosphate salt or a condensed phosphate salt alone may be used. The pH is usually kept between 6.0 and 7.5. The presence of the polyelectrolyte significantly improves the rate of dewatering that can be achieved with conventional filtration equipment (e.g., a rotary vacuum filter) during the processing of the pigment. Thus, the presence of polyelectrolyte during filtration decreases filtration costs, and the increased filtration rate compensates in part for the cost of the cationic polyelectrolyte. It should be noted that the amount of polyelectrolyte used in practice of the present invention is not selected to maximize settling or filtration rates since in practice of the invention the bulked structure must be capable of being formed to a clay-water system having useable viscosity after addition of a suitable quantity of deflocculating agent. In some cases, it will be necessary during manufacture to apply mechanical work to the bulked clay in the filter cake while adding a deflocculating agent in order to obtain a desired low viscosity. Filter cake solids vary with the equipment used and the level of vacuum applied. Solids also vary with the particle size characteristic of the clay. Generally, addition of polyelectrolyte flocculant usually decreases the solids content of the filter cake. The filter cake is washed with water to remove soluble matter. It has been found that use of hot water, e.g. water having a temperature above 100°F. and below the boiling point, is beneficial. Use of a hot wash has resulted in products having a lower Brookfield viscosity than was obtained when wash water was at ambient temperature. The use of a hot wash results in filter cakes having a reduced content of salts. For example, filter cakes having specific resistances ranging from 13,000 to 50,000 ohm-cm resulted from washes at 120-140°F. while unheated water in similar amount resulted in cakes having specific resistances of about 6000 ohm-cm. It has also been found that slurries prepared by adding dispersant to conventionally washed (cold water) filter cakes should be spray dried without aging the slurries for more than one or two days because high and low shear viscosity of spray dried pigments are adversely affected. When a hot wash is used, slurries can be aged for longer times, e.g. two weeks or longer, without detriment to the rheology of the pigment. By using a hot wash, pigments can be shipped in slurry form without an intermediate drying step. This is of significant economic benefit. In some cases, it is necessary to increase the solids of the filter cake to realize the desired reduction in Brookfield viscosity of the product, especially when the work input during blunging is low. For example, in the case of one bulked clay which produced a filter cake having a solids content of 55%, the desired reduction in viscosity necessitated addition of dry clay to build up to a solid content of 59% prior to spray drying before the mechanical work was effective. The dewatered and washed filter cake may be fluidized by adding a deflocculant and supplied for shipment in slurry form as mentioned above. Alternately, the filter cake can be fluidized by addition of a deflocculant and then spray dried to produce a dry so-called "predispersed" product in dustless form. Although aqueous suspensions of our bulked clay can contain added deflocculant to increase fluidity, these suspensions are not truly in deflocculated or dispersed condition because the bulked, flocced structure is retained. Thus, these slurries can be termed "partially deflocculated" slurries or suspensions. The amount of deflocculating (dispersing) agent used to fluidize the washed filter cake is typically less than conventionally used for secondary dispersion. Thus, secondary dispersant is generally used with coating grades of clay in amounts of 0.3% to 0.5% based on the dry clay weight. Dispersant levels much greater than 0.2% have been found to convert low viscosity slips of clays bulked as above to slips having high viscosity. After addition of dispersing agent, the filter cake cake is then subjected to controlled agitation to redisperse the clay particles. The resultant bulked polyelectrolyte treated clay product, after addition of a clay deflocculating agent, is used to form high solids (at least 60% clay solids) suspensions in water. These suspensions are then formed into aqueous coating colors suitable for applying on paper. Alternatively, the bulked product may be used as a filler for paper webs. The kaolin clay pigments bulked as described above are especially useful in preparing coating colors for coating lightweight publication papers, particularly magazine stock, to achieve coated papers having excellent opacity and printability. Coat weights of light weight coated publication papers are usually 3 to 7 lbs/3000 ft². The printability and opacity are generally at least equal (and usually superior) to that achieved by the commercially used blend of delaminated kaolin clay and calcined kaolin clay. Preferred pigments for use in the invention have the following properties: We believe such bulked clay pigments possess adequate shear stability to survive production and handling conditions such as described above, using conventional commercial processing equipment and also are sufficiently stable for use in high speed coaters used by the paper industry. In preparing coating colors, conventional adhesives or mixtures of adhesives are used with the deflocculated clay slip. For example, useful coating color compositions are obtained by thoroughly mixing with the clay slip from 5 to 20 parts by weight adhesive per 100 parts by weight of polyelectrolyte treated clay. Such a coating color, when used for coating lightweight publication paper, produces a product which has excellent opacity, gloss and printability. The term "adhesive" as used herein refers to those materials known for use in connection with paper pigments, which aid in binding the pigment particles together and, in turn, binding the coating to the paper surface. Such materials include, for example, casein, soybean proteins, starches (dextrins, oxidized starches, enzyme-converted starches, hydroxylated starches), animal glue, polyvinyl alcohol, rubber latices, styrene-butadiene copolymer latex and synthetic polymeric resin emulsions such as derived from acrylic and vinyl acetates. When the adhesive comprises a starch which is jet cooked in the presence of added bulking pigment, we believe the use of a mixture of nonionic surfactant and sodium polyacrylate will permit the steam jet cooking of this mixture and will avoid the development of extremely viscous, unworkable coating colors. Steam jet cooking of a coating color composition is described on a Canadian Patent No. 1,140,332. Typical temperatures are 225-325°F. The coating color compositions prepared in accordance with the present invention can be applied to paper sheets in a conventional manner. All particle sizes used in this specification are determined with the SEDIGRAPH® 5000 particle size analyser and are reported as equivalent spherical diameters (e.s.d.) on a weight percentage basis. In the examples, test results were obtained by the following TAPPI (Technical Association of the Pulp and Paper Industry) procedures for paper: 75° gloss - TAPPI Standard T480 ts-65. Value denotes the evenness or smoothness with which a coating lays on the surface of paper. B & L opacity - TAPPI Standard T425-M-60 G. E. brightness - TAPPI Standard T452-M-58 Furthermore, light scattering and gloss of pigments were determined in some instances. This was done by coating the kaolin clay suspensions onto black glass plates at a coat weight of 7.0-14.0 g/m² (expressed as dry clay). The reflectance of the coatings after drying in air at wavelengths 457 nm and 577 nm is measured by means of an Elrepho reflectometer. The reflectance values are converted by the use of Kubelka-Munk equations to light scattering values (m²/g). The light scattering values are a measure of the opacity potential of the clay because the higher values indicate that light rather thin passing through is reflected and scattered back. The higher the light scattering value, the higher the opacity potential of the clay. Reflectance is measured at two different wavelengths. The 457 na wavelength corresponds to the wavelength used in the TAPPI brightness measurement and the 577 nm wavelength to that used to measure opacity. In preparing slurries for measurement of high shear (Hercules) and low shear (Brookfield) viscosity, Engelhard Corporation procedure PL-1 was used. Brookfield viscosity was measured using TAPPI procedure T648 om-81 at 20 rpm using the #1 or #2 spindle; in some cases Brookfield viscosity was measured at 100 rpm using the #3 spindle. All slurries were formulated with optimum amount of dispersant, following the PL-3 procedure of Engelhard Corporation. Following are descriptions of PL-1 and PL-3 procedures. PL-1 is the standard laboratory makedown method for hydrous clays at 70% solids under high shear conditions. Hydrous clays may also be madedown at other solids such as 68% solids for delaminated clays utilizing this procedure and adjusting the amount of water needed. Equipment and Material Analytical balance Aluminum tins for weighing Electric, forced air oven Laboratory balance, accuracy ± 0.1 grams Waring Blendor® mixer (belt driven by 3/4 HP motor, with pulley to provide 10,500 RPM). 1000 ml and 600 ml unbreakable beakers 500 grams oven dry clay 214 grams deionized water Dispersant (as required), i.e. tetra sodium pyrophosphate (TSPP) or organic such as Colloids 211 Procedure for Preparation of 70% Solids Clay Slurry A. Formulation for 70% solids clay slurry Deionized Water 214.0 gms Mineral (O. D.) 500.0 gms Total..... 714.0 gms B. Determine the moisture content of the mineral to be used by drying a 3 gram sample in the oven for 30 minutes at 220°F. and cooling in a dessicator for 15 minutes before reweighing. C. Place 214 grams of distilled water in the Waring Blendor (subtract moisture in clay from 214 grams). If a dispersant is to be used, add it to the water and mix in the blender for 30 seconds. D. Weigh the oven dry equivalent of 500 grams of clay into a tared beaker. Add the 500 grams of clay to the water using a small scoop. After the addition of each scoop of clay to the water, "jog" the switch on the motor "off" and "on" momentarily to disperse the clay into the water. Do not allow the motor to attain full speed during the incorporation of the clay into the water. Only allow the blender to come to full speed after all the dry clay has been added. Excessive additional shear on the clay/water slip (particularily in the case of delaminated clays) will effect the reproducibility of rheological measurements on a given sample. E. When all the clay has been added to the water, scrape the clay on the sides of the blender into the slurry with a spatula. Let the slip mix under full agitation for 60 seconds. F. Transfer the slip to a tared 600 ml unbreakable beaker and cap tightly to prevent evaporation of water. (Aluminum foil provides a good "capping" material). G. Cool the clay slip to 80°F. and determine the final solids content. The solids should be within ± 0.2% or adjustment is necessary. Adjustment can be made if the percent solids is too high by the addition of water. However, if the percent solids is too low, the slip will have to be discarded and a new one made. H. Rheological properties of the slip should be measured and recorded in accordance with standard methods. Procedure for Determining Maximum Slurry Solids Maximum slurry solids is dependent on optimum dispersion. Therefore, the attainment of maximum solids requires prior knowledge of the optimum dispersant demand for the particular pigment under investigation. Follow PL-3, described hereinafter, for determining the optimum dispersant level before proceeding with the following steps. A. Follow the procedure outlined in steps C to G for the preparation of a 70% solids slurry, employing the previously determined optimum dispersant level (with some clays it may be necessary to start at slightly lower solids levels to produce a flowable mixture at optimum dispersant levels). B. Add an additional quantity of clay until a non-flowable mixture is produced by the blender. C. Add additional dry dispersant such as TSPP at the rate of 0.30% on the weight of the additional clay added in step B. Mix for 5 seconds. D. The slurry should fluidize with the addition of the dispersant. Repeat steps B and C until the slurry no longer fluidifies after the dispersant addition. E. The solids content at this point is recorded as maximum operable solids for this clay. This method determines the amount of dispersant to obtain minimum viscosity of clay. Optimum dispersion is determined by the PL-3 procedure which involves making small additions of dispersant to a slurry, mixing and then determining the Hercules and Brookfield viscosity. The dispersant level before the viscosity increases (becomes poorer) is the optimum dispersant level. The optimum dispersant level for Hercules viscosity may be different than the optimum Brookfield viscosity and therefore Hercules or Brookfield optimum should be specified. Equipment Modified Waring Blender (belt drives by 3/4 HP motor, with pulley to provide 10,500 RPM) Hercules Viscometer Brookfield Viscometer Talboy variable speed mixer Constant temperature bath Laboratory balance (0-10 grams) Deionised water Pigment (500 oven dried grams or 250 grams for calcined clay) Dispersant (inorganic or organic) Electric, forced air oven at 105 ± 3°C. Procedure Prepare hydrous kaolin by PL-1 method (supra). Add no dispersant for predispersed clay and minimum amount (about 0.2%) of dispersant for pulverized clay. B. Determine the percent solids of the sample by drying part of the sample in an oven. Solids should be 70 ± 0.2% for hydrous clay, 68 ± 0.2% for delaminated clay, 50 ± 0.2% for calcined clay and other solids as required. C. Determine the Brookfield viscosity and Hercules viscosity of the sample. D While mixing the sample using the Talboy mixer, add .05% dispersant based on pigment weight and continue mizing for five minutes. E. Determine the Brookfield viscosity and Hercules viscosity. F. Repeat D and E until the viscosity increases (becomes poorer). G. Optimum viscosity is the amount of dispersant added before the viscosity increases or there is no viscosity change. The solids, dispersant level and Brookfield and Hercules viscosity are reported at optimum viscosity. Hercules viscosity values reported herein were measured with Hercules Hi-Lo Shear Viscometers, Model ET-24-6. These instruments are equipped with a cup to contain the sample fluid and are supplied with a series of rotating bobs and spring sets which provide a variety of shear rate conditions. One Hercules viscometer was equipped with the "A" bob and was employed to operate with the 100,000 dyne cm/cm spring up to 1100 rpm for clay water slurries; the other was set to operate with a 400,000 dyne cm/cm spring up to 4400 rpm to measure viscosity of coating colors. Following are details of the "A" and "E" bobs. Bob Bob Height Bob Radius Cup-Bob Clearance S Value Max. Shear Rate @ 4400 rpm Shear Rate Factor (Factor X rpm) = Shear Rate) A 5.0 cm 1.95 cm 0.05 cm 0.00020 18196 sec.¹ 4.14 E 5.0 1.98 0.02 0.00008 45900 10.42 TAPPI Procedure T648 om-81 gives further description of the procedures used to measure high shear viscosity. It is common to report high shear viscosity of clay-water as either dyne-cm X 10⁵ torque at 1100 rpm bob speed or as bob speed in rpm at which the maximum torque of 16 X 10⁵ dyne-cm was obtained. Similarly, the coating color viscosity is reported as either dyne-cm x 10⁵ torque at 4400 rpm bob speed or as bob speed in rpm at which the maximum torque of 64 X 10⁵ dyne-cm was obtained. Viscometers were operated in the manner summarized below: 1. Set the graph and pen in place on the recording drum (pen is placed on origin on graph paper). 2. Remove the cup and bob from the water bath at 80°F. and dry. 3. Pour 28 ± 2 cc. of the fluid to be tested into the cup and set in place on the viscometer. Use of a syringe will frequently facilitate filling the cup. 4. Attach the bob by rotating it counter-clockwise making it only finger tight, then imerse it in the fluid cup to its limit. The fluid should come up to the top of the bob. If not, then more fluid must be added until it covers the bob. 5. Start the viscometer motor (lower left front of viscometer). 6. Press the "AUTO" switch on the control panel. The pen will proceed to draw a graph of shear rate versus shear force (torque). If the viscometer reaches its maximum rpm set point, the pen will automatically return to its starting point. However, if the pen goes beyond the maximum allowable torque before reaching maximum rpm, the viscometer will automatically shutdown and the recording drum will have to be returned to its original position using the crank handle. The precision is based on a dyne-cm X 10⁵ reading at 1100 rpm and rpm reading at 16 dyne-cm x 10⁵ because these are the values reported for products. The 95% confidence level for the precision for three operations at two different viscosities follows: Average Precision 4.4 dyne-cm X 10⁵ at 1100 rpm 16.8% 500 rpm at 16 dyne-cm X 10⁵ 21.4% In measuring printing properties by the so-called 75° Gloss Ink Holdout Test, the procedure used was one described in a publication by Otto P. Berberich, TESTING PRINTABILITY OF PAPER AND BOARD WITH INK - III, November 1957 IPI. The procedure gives results relative to the printing qualities on a letter press proofpress using halftone printing plates. The K & N Ink Holdout Test entails applying an excess of heavy bodied black pigmented printing ink to coated paper, removing the excess and ascertaining the contrast between the image and the background. In measuring printability of the paper coated with the coating color, the Helio test was used. This test is widely used to evaluate printability by the gravure method. In the test, the coated sheet is printed with a gravure cylinder, which has a pattern of ink holding cavities that decrease in diameter from one end to the other. Thus the test print has large dots at one end and small ones at the other. Skipped dots are counted starting at the large-dot end, and the print quality is reported as the distance in millimeters from the start of the test print to the 20th missing dot. For a given coat weight, the longer the distance in millimeters the better the printability of the coated paper. The examples describe results for making down slurries of experimental and control pigments using laboratory and pilot plant procedures. In the laboratory procedure, Waring Blendor® mixer Model 31 BL 46 was used with a 40 oz. blender jar and cover and a Variac power supply control. An amount of dispersant (typically 0.25% Colloid 211 or 0.25% TSPP based on the dry weight of the pigment) is dissolved in water calculated to provide a 62.0 - 62.5% solids slurry containing 300 g. of pigment. Three hundred (300) g of pigment was added gradually at moderate speed. When all of the pigment was added, the blender was run for one minute at 50 volt Variac setting. Pilot plant makedown was performed with a Cowles mixer (10" vessel dia, 4" blade dia, 3300 rpm blade speed, 3455 ft/min tip speed). Dispersant was added to water, followed by addition of pigment to water, as in the laboratory procedure, and mixed at slow speed. The mixer was then run at 3300 rpm for 5 minutes. EXAMPLE I The kaolin pigments used in this example were prepared from a sample of a deflocculated aqueous suspension of Georgia kaolin clay. The deflocculating agent was sodium silicate. Solids content was about 35%. The particle size distribution of the clay in the deflocculated aqueous suspensions was 55-60% less than 2.0 micrometers, 1.3-1.6 micrometers median diameter and 10-11% less than 0.3 micrometers diameter. This suspension was diluted with water to between 15 and 20% solids. The diluted suspension was separated by gravity sedimentation to provide supernates containing particles of 0.70 micrometers ("Coarse"), 0.62 micrometers ("medium") and 0.55 micrometers ("fine") median particle size (e.s.d.). The pH of separated suspension fractions was 8-10. It was reduced to 7.0 with 10% aqueous sulfuric acid. A commerically available dimethyl diallyl quaternary ammonium chloride polymer (Polymer 261 LV) concentrate was diluted to 1% solids and added to the separated suspension fractious with stirring for 5-10 minutes, and the pH of the fractions was adjusted to 2.5 with sulphuric acid. The "fine" fraction was treated with 0.07% and 0.09% polymer and the "coarse" fraction with 0.07% polymer. The percentages are given on the basis of dry polymer to dry clay. The treated suspension was bleached with sodium hydrosulphite by its addition to the fractions at the rate of 10 lbs. per dry ton of clay. After standing 30 minutes, the bleached fractions were vacuum filtered, and the filter cakes were washed with cold water until the filtrate measured 5000 ohm-cm specific resistance. The washed filter cakes were then deflocculated with tetrasodium pyrophosphate by kneading the dry salt into the filter cake with a spatula. The amount of phosphate used was 0.1% based on the weight of dry clay. Kneading was continued until the wet filter cake became pourable at which point it was transferred to a Waring Blendor® mixer. The filter cake was then formed into a fluidized suspension by agitation in the Waring Blendor mixer. The resultant clay suspensions had solid contents of 55 to 62%. The fluidized clay suspensions were spray dried and the spray dried clays were formed into coating colors (56% solids) by mixing 100 parts of the treated clay with 7 parts of cooked hydroxyethylated starch (Penford Gum 280, 30% solids) and 4 parts styrene-butadiene latex (Dow Latex 620, 50% solids). All quantities in the preceding sentence are expressed in terms of dry ingredients. The colors were coated on the wire side of a 24 lb. lightweight paper basestock using a coater equipped with an air pressure loaded coating blade so that the coatings could be applied in the range of 3 to 6 lbs./3000 ft² ream. The sheets were conditioned at 50% relative humidity and 72°F and were calendered on two different laboratory calendering units: Unit A, 2 nips at 140°F and 230 pli; and Unit B, 3 nips at 140°F and 500 pli (pounds per linear inch). The opacity and gloss of the calendered sheets were determined using TAPPI (Technical Association of the Pulp and Paper Industries) procedures. Opacity was determined in accordance with TAPPI Standard T 425-M-60 and Gloss in accordance with TAPPI Standard T 480ts-65. Opacity and gloss are recorded in percent, the higher the percent the better the opacity and gloss. The opacity, gloss and printability measurements are summarized in Table I below. The data in Table I are linear regression values based on measurements at three different coat weights, and then calculated for the 5 lb./ream coat weight. For purposes of comparison, a control color was prepared wherein the pigmentation consisted of 90 parts LITECOTE® clay and 10 parts ANSILEX® clay. LITECOTE is a commercial delaminated pigment with a median equivalent spherical diameter of 0.70 micrometers. ANSILEX is a commercial calcined pigment with a median equivalent spherical diameter of 0.80 micrometers. The solids content of this coating color was 57%. Coating and testing procedure was identical to those used with other pigments in EXAMPLE I. Properties of Sheet Coated with Coating Color Containing Polymer Treated Clay Clay Particle Size Polymer Conc. (%) Calender Unit A Calender Unit B Sheet Opacity (%) Gloss (%) Helio-Printability (mm) Sheet Opacity (%) Gloss (%) Helio-Printability (mm) Fine 0.07 88.3 49.1 63 87.1 49.3 87 Fine 0.09 88.4 46.8 63 86.8 47.7 96 Coarse 0.07 87.8 40.3 63 86.9 43.1 96 Control -- 87.4 48.0 55 86.0 47.8 83 Data in TABLE I indicate that the experimental pigments surpassed the control (LITECOTE/ANSILEX) in printing quality and opacity, and generally produced sheet gloss comparable to that of the control. The data also show that the coarse clay tends to lose gloss but maintains printability. The data also show that raising the Polymer 261LV level to 0.09% tended to maintain the bulking effect. However, clay slips and coating colors prepared using clays treated at this concentration level tend to exhibit an adverse increase in viscosity. EXAMPLE II Part A For purposes of further comparison, the bulking of "fine" (0.55 micrometer) particle size kaolin clay was attempted using a variety of commercially available amines, amine salts quaternary ammonium salts and cationic polymers commercially used for the flocculation of particulate matter suspended in water. The procedure of EXAMPLE I used to prepare the bulked kaolin clay with Polymer 261LV was repeated with each of the flocculants including Polymer 261LV. Bulking was rated by estimating the increase in thickening of the clay dispersion containing 25% clay solids after the addition thereto of 0.07% of the flocculating agent, the percentage being based on the weight of the dry clay. If there was no observable thickening of the dispersion after the addition thereto of the individual flocculating agent, the bulking effect was rated "none." If a light creamy consistency was imparted, the bulking effect of the flocculant was rated "slight." If a thickening of the dispersion occurred which was observable when the dispersion was poured, the bulking effect was rated "some." The bulking effect caused by the Polymer 261LV was rated "considerable" because it nearly solidifies the slurry so that it would not pour. The bulking ratings of the various flocculants evaluated in the comparative study are recorded in TABLE II below: Results reported in TABLE II indicate that among the materials listed, polydimethyl diallyl ammonium chloride was unique in the bulking of the kaolin clay dispersion at the concentrations evaluated in these tests. Part B Further testing was carried out to evaluate the ability of various commercial cationic polymers materials supplied for use as flocculating or coagulating agents to flocculate kaolin clay suspensions and to produce dried opacifying pigments capable of being formed into clay-water solids of about 62% solids which have acceptable high and low shear rheology. The kaolin clay used in the testing was a fraction of a crude mined in central Georgia (Washington County), the clay fraction having been selected to have a desirable particle size distribution using Calgon 261 LV polymer at the 0.08% addition level. Particle size of the fraction was 90% ± 2% by weight finer than 2 micrometers; 50% by weight finer than 0.57% ± 0.03% micrometers and no more than 20% by weight finer than 0.3 micrometers. The clay fraction was provided as a 20% solids slurry and contained a mixture of sodium silicate and sodium carbonate as the deflocculating agent. The pH was about 7. The cationic polyelectrolytes used in the testing, in addition to Calgon 261 LV, were materials supplied under the following registered trademarks: NALCOLYTE 7107, NALCOLYTE 8102, NALCOLYTE 8100, NALCOLYTE 8101, and NALCLEAR 7122. In carrying out the settling tests, portions of the 20% solids slurry were diluted in graduated cyclinders to about 10% solids by adding sufficient water to form 100 ml of diluted slurry (10 g dry clay/100 ml diluted slurry). The contents of each cyclinder were mixed by covering its mouth and rapidly inverting the cylinder several times. The effectiveness of the various treatments in bulking (flocculating) the suspensions was investigated by observing the settling characteristics of each suspension over a period of time. The concentrations and the results after 26 hours settling are summarized below for those cationic materials which exhibited settling characteristic when added at the given level similar to Calgon 261 LV at the 0.08% addition level. At all time intervals between 1 and 26 hours, slurries treated with these agents using the amounts shown below exhibited settling characteristics similar to or slightly better than those measured with Calgon 261 LV at the .08% level. Polymer Quantity by Weight mm of Supernatant Liquid Clarity of Supernatant liquid 7107 0.25% 30 Clear 7122 1.00% 32 Clear 8100 1.00% 29 Clear 8101 1.00% 29 Clear 8102 0.50% 30 Clear Calgon 261 LV 0.08% 29 Clear Based on these results, evaluations of pigments were made to determine opacification (light scatter) and ability to be dispersed in water at about 62% solids to form fluid slurries. Rheology of dispersed slurries was evaluated at a lower solids concentration when a 62% solids slurry could not be formed. The sample of clay used in these tests was obtained from the same mine and processed in the same way used to produce a fractionated clay having the same particle size distribution as the clay used in the settling experiments described above. The pigments were prepared by adding polyelectrolyte to a 20% solids clay slurry at pH 7, acidification to pH 3 with sulfuric acid, addition of K-Brite Brand sodium hydrosulfite bleach in amount of 8 pounds per ton of dry clay, aging for 30 minutes followed by filtration, and washing the filter cake with cold water. After drying in an oven and pulverizing, each pigment was dispersed at 62% solids with the addition of 0.025% (dry clay basis) of Colloid C-211 sodium polyacrylate dispersant by agitating in a Waring Blendor mixer at a 50 volt setting for one minute. Then further polyacrylate was added, if necessary, to reach minimum Brookfield viscosity at 20 rpm. The results are summarized below: Effect of Bulking Kaolin Clay with Various Cationic Polyelectrolytes on Optical and Rheological Properties Polymer, % Slurry Properties and Composition Black Glass Scattering m²/g % Solids pH Brookfield Viscosity Hercules Endpoint Viscosity @ 457nm @ 577nm cp. 20rpm cp. 100 rpm None ** ** ** ** ** .128 .093 Calgon 261 LV, 0.08% 62.5 7.2 50 60 560/16 .153 .127 Nalcolyte 7107, 0.25% 62.2 7.2 50 59 1100/1.2 .150 .102 Nalcolyte 8101, 1.0% 62.0 7.2 75 87 410/16 .178 .134 Nalcolyte 8100, 1.0% 62.2 8.0 100 103 655/16 .185 .136 Nalcolyte 8102, 0.5% 61.1 7.0 55 80 500/16 .189 .138 **Not Determined. When similar tests were carried out with a sample of ASP® 100 hydrous kaolin, the results were in general similar; however, scatter at 457 and 577 nm was lower. The particle size of this clay was 92% by weight finer than 2 micrometers, 50% by weight finer than 0.4 micrometer, and 35% by weight finer than 0.3 micrometers. EXAMPLE III For purposes of still further contrast, the procedure of EXAMPLE I was repeated with the exception that the kaolin clay was not treated with Calgon Polymer 261LV prior to its incorporation in the coating color. The clay used in this test was the "fine" kaolin clay of EXAMPLE I. Polymer 261LV was added to the coating color at a concentration of 0.07% by weight based on the weight of the untreated clay already incorporated in the coating color. When this comparative coating color was coated on paper base stock and calendered in Unit A, in accordance with the procedure of EXAMPLE I, gloss of the calendered sheet was lowered by 3 points. Opacity was lowered by 0.6 points relative to sheets of equal coat weight prepared from the same clay treated with 0.07% polymer as described earlier in EXAMPLE I, indicating that incorporation of Polymer 261LV in the coating color in this manner did not produce the desired improvement. EXAMPLE IV The procedure of Example I was followed to prepare filter cakes containing kaolin particles of fine, medium and coarse particle size treated with 0.07% by weight Polymer 261LV based on the weight of the clay solids. The filter cakes were formed into suspensions by agitation in a Waring Blendor® mixer in the presence of added tetrasodium pyrophosphate in sufficient quantity to yield a fluid dispersion for 1 minute using either low or high shear conditions. Low shear conditions were obtained with a setting of 40 on the rheostat which controlled the power input to the mixer and high shear conditions with a rheostat setting of 100. The Brookfield and Hercules (high shear) viscosities and the light scattering and gloss of the clay suspensions prepared under high and low shear conditions are recorded in TABLE III below. It is believed that dispersant addition level, which was not measured, was not optimum. The procedures of EXAMPLE I were also repeated to prepare coating colors from the suspensions of polymer treated clays ("fine", "medium", and "coarse" fractions) by mixing 100 parts of the clay slips with 7 parts hydroxyethylated starch and 4 parts styrene butadiene latex (under low and high shear conditions). The amounts of the ingredients used in the formulation of coating colors are given on a dry weight coating basis. The control coating color was prepared in the same way as in EXAMPLE I. The Brookfield and Hercules viscosities, light scattering and gloss of the coating colors containing the polymer treated clay slips are recorded in TABLE III below. Rheology, Light Scattering and Gloss of Water Suspensions of Polymer 261LV Treated Clay Clay Particle Size Shear Solids (%) Viscosity Gloss % Black Glass Coating-Light Scattering Brookfield (20 rpm) (cps) Hercules (rpm) S₄₅₇ (m²/g) S₅₇₇ (m²/g) Fine Low 61.8 488 165 60 0.186 0.130 Fine High 61.7 88 473 62 0.178 0.127 Medium Low 61.4 188 283 58 0.182 0.128 Coarse Low 61.8 225 --- 51 0.160 0.115 Rheology, Light Scattering and Gloss of Coating Color Clay Particle Size Shear Solids (%) Brookfield (20 rpm) (cps) Hercules Viscosity dyne cm X 10⁵ Gloss % Black Glass Coating-Light Scattering S₄₅₇ (m²/g) S₅₇₇ (m²/g) Fine Low 57.6 8450 56 34 0.182 0.142 Fine High 57.7 8200 54 36 0.182 0.143 Media Low 57.2 5200 48 24 0.172 0.136 Coarse Low 57.7 6850 -- 19 0.139 0.110 Control --- 57.9 2475 44 -- 0.130 0.100 The data recorded in TABLES III and IV indicate that regardless of particle size, the bulked clays have usable Brookfield and Hercules color viscosities; Brookfield viscosities are lower at high shear than at low shear indicating that shearing reduced the viscosity of the slips of the dialkyl diallyl quaternary ammonium salt polymer treated clay. The light scattering and gloss values recorded in Tables III and IV indicate that the bulking structure was not destroyed by high shear and that the properties of the Polymer 261 LV treated clay particles when dispersed under high shear conditions were only minimally altered when compared to those values of the Polymer 261 LV treated clay dispersed under low shear conditions as evidenced by the almost total lack of change in the light scattering and gloss values at S₄₅₇ and S₅₇₇. EXAMPLE V Coating colors were prepared using clay slips of 0.55 micrometer and 0.62 micrometer size kaolin clay treated with 0.07% Polymer 261 LV under high and low shear dispersion conditions following the procedure of EXAMPLE IV. The colors were coated on paperbase stock to a coat weight of 5 lbs/3300 ft³ ream. The coated sheets were calendered in steps at 140°F and 500 pli. The steps are designated as "nips", (1,2,3 nips). The opacity of the calendered sheets as well as an uncalendered sheet was determined in accordance with TAPPI T 425-M-60 and the gloss of the sheets was determined in accordance with TAPPI T480ts-65. The LITECOTE/ANSILEX control was also prepared and tested as in the previous example. The opacity and gloss results are recorded in TABLE V below. The data in Table V, like that of TABLE I, supra, are linear regression values at 5 lb/ream coat weight calculated from measurements at three different coat weights. Effect of Shear Conditions on Properties of Sheet Coated With Coating Colors Prepared from Polymer 261 LV Treated Kaolin Clay Clay Shear Cond. Color Solids % Uncalendered Calendar Unit B Op Gl. 1 Nip 2 Nip 3 Nip Op. Gl. Op. Gl. Op. Gl. Fine Low 57.6 91.3 10.0 89.3 31.0 86.7 41.6 86.2 47.7 Fine High 57.7 91.2 10.3 88.0 31.8 86.8 41.7 85.7 49.1 Medium Low 57.2 91.1 7.3 88.1 26.8 86.2 37.4 85.6 44.2 Control 57.9 90.2 9.9 87.7 29.2 85.2 39.3 84.7 45.5 The data in Table V indicate that shear conditions do not affect significantly the properties of coating colors prepared by using Polymer 261 LV treated clay and that the improved properties of opacity and gloss exhibited by the polymer treated clay are maintained under supercalendering conditions regardless of dispersion shear. It should be noted that opacity and gloss of supercalendered sheets normally decrease as the base clay is made coarser. EXAMPLE VI The procedure of EXAMPLE I was followed to prepare a filter cake containing kaolin clay particles of fine (0.55 micrometer) particle size treated with 0.07% by weight Polymer 261 LV (based on the weight of the clay solids). The filter cake was formed into a suspension (55% solids) by agitation in a Waring Blendor mixer for 1 minute using high shear conditions. The Polymer 261 LV treated clay suspension was added to a groundwood pulp furnish, which had been previously pulped to a Canadian Standard Freeness of 125 milliliters and a fiber consistency of about 2.7 percent by weight, to produce handsheets containing a variety of net mineral contents (NMC) ranging from 4.57 to 14.28%. The pulp/clay blends were mixed in a laboratory disintegrator until homogeneous suspensions, diluted to 0.25% fiber consistency, were obtained. Handsheets were formed from the pulp/clay suspensions using a M/X Systems, Inc. Miniformer at a target basis weight of 35 lbs/3300 square feet (52.1 grams per square meter). To ensure adequate clay retention, a cationic polyacrylamide retention aid sold under the trademark designation ACCURAC 620 was added to the stock in the Miniformer headbox at a concentration of 0.5 pounds per ton of fiber. The handsheets were pressed and dried on the Miniformer and were conditioned at least 24 hours at 73°F, 50% relative humidity. Thereafter the brightness and opacity were measured. Handsheets which had been conditioned an additional 24 hours at 73°F, 50% relative humidity were calendered (B) through two nips at 500 pli. For purposes of control, the procedures were repeated using no filler (Control A). For further purposes or control, the procedures were repeated using an untreated kaolin clay (HT" clay), which has a median particle size of about 0.7 micrometers and is about 80% by weight finer than 2 micrometers (Control B). The brightness and opacity results, adjusted to a basis weight of 52.1 g/m², are summarized in TABLE VI below. The data in TABLE VI indicate that the use of Polymer 261 LV treated kaolin clay as a filler produced a sheet that was relatively high in brightness, had relatively high opacity and in most cases did not lose these properties when the paper was supercalendered. EXAMPLE VII Tests were carried out to evaluate the utility of a bulking pigment of the invention in preparing offset printed lightweight coated paper. The bulking pigment was prepared substantially as described in EXAMPLE I from a sample of Georgia kaolin clay that was about 85% by weight finer than 2 micrometers and about 22% by weight minus 0.3 micrometers. Median particle size was about 0.6 micrometers. Calgon 261 LV polymer was added in amount of 0.07%, dry weight based on the weight of the clay. After addition of polymer, the suspension was flocculated by addition of acid, bleached, dewatered and dried. The sample was slurried at 62.5% solids in the presence of 0.1% by weight of tetrasodium pyrosphosphate, based on the dry clay weight using low shear conditions. A coating color was prepared, using conventional procedures and adding the following ingredients in the order listed: Parts by weight (dry weight basis) 100.0 Pigment 8.0 Cooked Penford Gum 280 Starch 8.0 Dow 640A Latex 0.8 Sunrez 666 0.5 Nopcote C-104 The pH of the coating color was adjusted to 8.0 with ammonium hydroxide solution The coating color was applied to 24 lb. St. Regis offset base stock by a Keegan puddle blade coater to the wire side at a range of coat weights by varying the blade pressure. The coated papers were calendered prior to testing by using the Unit B calender under conditions of 2 nips, 250 pli and 140°F. Optical and printing properties were measured by standard procedures. For the purpose of comparison, the general procedure was repeated using as control pigments, a coating grade of kaolin clay supplied under the trademark LVHT as well as 50/50 (wt.) mixture of LVHT and LITECOTE clay. We believe that these clays are representative of clay pigments used to prepare offset grades of coated paper. TABLE VII summarizes the results obtained by testing the rheology of coating colors containing the experimental bulked pigment and the clay evaluated for purposes of comparison. TABLE VIII summarizes the results of optical and printing properties of coated sheets. Viscosity data reported in TABLE VII demonstrate the higher viscosity of the experimental pigment color. The data in TABLE VIII demonstrates the bulking effect of the experimental pigment which was evident by its good performance in opacity, porosity, K&N ink receptivity and print-through. EXAMPLE VIII The following test indicates how viscosity increases can be used to determine when an effective amount of polymer is added. The results of the test also confirm the belief that Calgon 261 LV polymer functions to flocculate high solids dispersions of hydrous kaolin clay. The clay used in the tests was ULTRAGLOSS 90® clay, a predispersed, ultrafine particle size kaolin clay, 98% by weight of the particles being finer than 2 micrometers 90% by weight being finer than 1 micrometer and median particle size of about 0.3 micrometers. The clay was provided as a spray dried product containing about 0.35% by weight of tetrasodium pyrophosphate which was added to a slip of the clay prior to spray drying. Calgon 261 LV was added in increments to a 65% solids deflocculated suspension of the clay (700 g clay.) This solids concentration was used to facilitate the observation of the thickening effect of the polymer addition. Brookfield viscosity (20 r.p.m.) was measured after each addition until the desired total of 0.07% dry weight of polymer was added based on the dry weight of the clay. Initial additions appeared to slightly decrease in viscosity. However, when about 60% of the amount generally effective to produce a bulked clay product using fine clay was added, viscosity began to increase and continued to increase until the total polymer addition was 0.07% (dry weight) based on the dry weight of the clay. The data is in TABLE IX. Effect of Addition of Calgon 261 LV Polymer on Viscosity of High Solids Deflocculated Clay Suspension Volume of Total Added (1% Solution of Polymer 261 LV) Brookfield Viscosity, cp 0 ml 180 10 ml 164 20 ml 152 30 ml 186 40 ml 272 50 ml 400 EXAMPLE IX The following is an example carried out using production scale equipment. A high purity kaolin crude clay from a deposit in Washington County, Georgia, known as North Jenkins crude, was degritted, dispersed in water with sodium silicate having a Na₂O/SiO₂ weight ratio of about 3/1 and sodium carbonate. The suspension was then fractioned in a centrifuge to 87% finer than 2 micrometers. The median particle size of the fractionated suspensions was 0.59 ± 0.03 micrometers; weight percentage finer than 0.3 micrometers was 17%. Solids were about 20% and pH about 7. The suspension was then passed through a high intensity magnetic separator magnet for purification. Calgon 261 LV polymer was added to the suspension of purified clay at the 0.08% level based on dry weight of clay. The polyelectrolyte was added as an aqueous solution of about 2% (wt.) concentration. The pH was adjusted to about 4 to 4.5 by addition of sulfuric acid and the sodium hydrosulfite (Na₂S₂O₄) bleach was added in amount of 6#/ton of clay. The slurry was then filtered on a rotary vacuum filter to produce a filter cake having 55-60% solids. The filter cake was throughly washed with cold water and dispersed by adding tetrasodium pyrophosphate in amount of 0.1% based on the dry clay, followed by kneading. The pH of the fluidized cake was adjusted to 6.5 - 7.0 by addition of sodium hydroxide. The suspension was then dried by spray drying. Using this crude, desired properties were: The scattering values shown above for the experimental pigment are two times greater than typical No. 1 grades of domestic hydrous coating clay. When such an experimental pigment is used as the sole coating pigments in offset paper coating formulations at 3 to 6 lbs/3300 ft² coat weights, these scattering values translate to sheet opacities comparable to those normally obtainable with paper coatings containing from 5 parts by weight of TiO₂ or 10 parts calcined clay. In addition, the greater hiding of the basestock can result in coated offset paper brightness comparable to there obtainable using coating clay having higher brightness. Pigments of the invention can have higher brightness values than those mentioned above provided the clay feed to which polyelectrolyte is added has a higher brightness and/or colored impurities are removed by flotation or other means. The viscosity of dispersed clay-water slurries of pigments prepared from this and similar fractions of crude kaolin is typically intermediate that of standard delaminated clay and fine particle size calcined clay used in paper coating. This is demonstrated by the following summary of typical properties: It has been found that makedown is best at 62-63% maximum solids for dispersing. Higher solids are possible but difficult and can yield high Brookfield viscosities. The rheology, scatter and gloss of the spray dried pigments will vary with solids of dispersion, amount and species of additional dispersant, if any, and pH. Also, the amount of work input used to prepare the pigment slurry before and after spray drying will affect these properties. The effect of some of these variables is shown by data for the pigment prepared is this example with 0.08% Calgon 261 LV. Makedown was by the laboratory procedure described above. EXAMPLE X The kaolin pigments used in this example were prepared using laboratory scale equipment from a sample of a deflocculated aqueous suspension of degritted, previously fractionated Georgia kaolin clay. The crude clay from which the degritted clay was obtained was from the Scott mine, Washington County, Georgia. The degritted clay had the following particle size distribution: 82% < 5 um; 68% < 2 um; 52% < 1 um; 50% < 0.95 um (weight median size); 25% < 0.50 um; 4% < 0.3 um. The degritted clay as received is at about 35% solids and contained sodium silicate as a deflocculating agent. This suspension was fractionated in conventional manner in a centrifuge to prepare three particle size fractions as follows: 79% < 2 um: 83% < 2 um; 90% um. The particle size distribution the 83% < 2 um fraction was 50% < 0.6 um and 18% < 0.3 um. The pH of the fractions was adjusted to 4.5 with sulphuric acid and bleached with sodium hydrosulphite by its addition to the fractions at a rate corresponding to 4 pounds per ton of dry clay. Calgon Polymer 261 LV concentrate, diluted to 1% concentration, was added to each of the separated suspension fractions with moderate stirring for 5-10 minutes. Each fraction was treated with the polyelectrolyte in amount to result in addition of 0.08%, 0.12% and 0.15% polyelectrolyte. The percentages are given on the basis of dry polymer to dry clay. In all cases, the suspensions thickened more than the flocculation induced by acid and bleach addition. The treated slurry appeared to have "creamy" consistency. After standing 30 minutes, each bleached and treated fraction was vacuum filtered, and the filter cakes were washed with cold water until the filtrate measured at least 5000 ohm-cm specific resistance. A portion of each of the nine washed filter cakes was then deflocculated with either tetrasodium pyrophosphate in amount of 0.025% based on the dry clay weight or sodium polyacrylate, Colloid 211, in amount of 0.025% based on dry weight of the clay, by working the 40% solution of the deflocculant into the filter cake with a motor driven paddle agitator. Agitation was continued until the wet filter cake became pourable. The fluidized clay suspensions were spray dried in conventional manner. The dried pigments were redispersed in water with a Waring Blendor mixer. (Model 31 BL 46). The procedure used was to dissolve the dispersant in water, and add the pigment gradually to the water while operating the mixer at moderate speed. When all pigment was added, the blendor was run for one minute at 50 volts Variac setting. The resultant clay suspensions had solid contents of about 62%. Viscosity of the spray dried clays was measured using the Brookfield instrument at 20 rpm and the Hercules viscometer ("A" bob). Light scattering was also tested at 457 nm and 5377 nm by the black glass method. The results are reported in Table X. Data in Table X show that addition of the quaternary ammonium polyelectrolyte at the 0.03% level resulted in a pigment having lower opacification than when used at higher levels. At the 0.15% or 0.13% addition level, scatter was better than at lower levels but low shear and/or high shear were higher than desired. Generally, the best compromise between the measured optical property (scatter) and rheology was achieved at polyelectrolyte addition levels of 0.06% and 0.08%. The data in Table X also appear to indicate that light scatter was affected by the particle size of the clay. EXAMPLE XI Some experimental pigments prepared under EXAMPLE X were further evaluated. Another sample (Sample 4) was prepared from the same 90% < 2 um fraction, utilizing the same procedures except that 0.08% Calgon 261 LV was added before spray drying. Thus Samples 2 and 4 were prepared from the same clay using the same amount of polyelectrolyte but in Sample 2 polyelectrolyte were added before filtration and in Sample 4 polyelectrolyte was added after filtration. The samples evaluated are identified as follows: Sample No. % Calgon 261 LV % < 2 um clay in Feed 1 0.08% 80 2 0.08% 90 3 0.15% 83 4 0.08% 90 Experimental pigments were made down to 62.0% solids slurries and slurries having minimum Brookfield viscosity were obtained by adding a suitable amount of Colloid 211. These slurries were made down in a Waring Blendor at 40 volts for one minute. Brookfield and Hercules viscosities were measured using procedures described above. The coating colors were prepared based on the following rotogravure formulation: Pigment 100 Penford Gum 7 Dow Latex 620 A 4 Nopcote C-104 0.5 Coating colors were made down to approximately 57% solids. The pH of each color was adjusted to 8.0 with ammonium hydroxide. Brookfield and Hercules viscosities were measured using standard laboratory procedures. It was necessary to dilute the color containing the pigment prepared with addition of 0.15% Calgon 261 LV to 56% solids because Brookfield viscosity of a 57% solids color was too high. The wire side of St. Regis rotogravure basestock was coated with each coating color on the Keegan blade coater at three coat weights. Dewatering, typical of pigments of this type, was observed during the application of all colors containing experimental pigment. It was most severe with the pigment with 0.15% Calgon 261 LV. The coated sheets were dried in a rotary dryer and conditioned overnight at 72°F. and 50% relative humidity. The sheets were then weighed and coat weights determined. When the required coat weights were obtained, the sheets were calendered through two nips at 140°F. and 250 pli. Calendered sheets were conditioned overnight at 72°F. and 50% relative humidity and tested for gloss, Elrepho brightness, opacity and Heliotest. The rheology of clay-water suspensions of each pigment were compared. The results appear in Table XI. The slurry of pigment to which 0.15% Calgon 261 LV was added had poor high shear rheology, possibly due to insufficient shear for this treatment level during makedown. The coating color of this pigment also had a high Brookfield viscosity at 57% solids. Dilution to 56% solids still yielded a high Brookfield viscosity. Optical properties of calendered sheets coated with experimental pigment and the control were measured. The control consisted of a blend of 90% Litecote and 10% Ansilex The gloss of both samples prepared from fine feed is equal to or greater than the control at all coated weights. Pigments made from coarser feed gave lower gloss than the control. Elrepho brightness of the experimental pigments was equal to or greater than the control at low coat weight. Rotogravure printability and opacity of experimental pigments was same or better than the control at all coat weights. It was found that Sample 2 prepared from fine feed and 0.08% polyelectrolyte gave gloss, opacity and Heliotest values greater than the control. Elrepho brightness of coated sheets was equal to or greater than the control at 3.9 and 6.1 pounds per 3300 square foot but less than the control at 5 pounds per 3300 square foot. The overall performance of this pigment was superior to the other experimental samples in the study and generally equal to the control. Sample 4 in which polyelectrolyte was added after filtration and before spray drying was overall inferior to Sample 2. EXAMPLE XII Two samples of kaolin clay treated with 0.08% Calgon 261 LV polymer (EXAMPLE X) were made down in water at 62.2% and 64.2% solids at optimum conditions (dispersed with 0.025% Colloid 211). These samples were placed in a shaker water bath at 100°F. The shaking frequency was slow at about 100 cycles per minute with the amplitude of about 7 cm. Viscosity and black glass scattering were measured at the beginning and every week thereafter. It was found that light scattering increased but high shear and low shear viscosity also increased with prolonged storage at elevated temperature. The slurries had a tendency to thicken, but they could be mixed with a spatula to a workable and measurable consistency. It was subsequently found that the use of hot (120-140°F.) water to wash filter cakes obviated the tendency of the slurries to thicken during storage. Attempts were made to evaluate changes in the particle size distribution curves of clays after they were bulked. These attempts have not yielded clearcut results. Those skilled in the art are aware of the fact that particle size distribution curves of clays are obtained by testing deflocculated aqueous suspensions. The rate of shear used to prepare deflocculated aqueous suspensions of bulked clays of the invention strongly influences the observed particle size distribution of the bulked clay. Furthermore, when using the SEDIGRAPH analyzer, defloculated clay suspensions being tested are diluted and subjected to vibration in a sonic bath. Such treatment could conceivably change the particle size distribution of a bulked clay by breaking down assemblages. In general, such testing indicates that bulked clay products of the invention are coarser than the clay from which the bulked clay products are derived at least in the fine article size ranges. For example, there generally appears to be a 50% reduction in the weight percentage of particles finer than 0.3 micrometers. Starting clay, the particles of which are about 20% by weight finer then 0.3 micrometers, usually produces bulked products which when sheared at a low shear rate (Waring Blendor mixer with a variac setting of 30-40 volts) appear to be about 10-11% by weight finer than 0.3 micrometers. Changes in size distribution of particles larger than 0.3 micrometer are generally less than the accuracy limit of the SEDIGRAPH instrument. EXAMPLE XIII When a bulked pigment obtained by treating kaolin clay with Calgon 261 LV polymer is dispersed in water with a polyacrylate or polyphosphate dispersant and the resulting dispersed aqueous slurry is heated, the dispersed clay water slurry thickens at about 60°C. This occurs when such dispersants are either added to the washed filter cake obtained during processing or if the dispersants are added to previously spray dried bulked clay. However, if this filter cake pigment is dispersed with a mixture of polyacrylate and nonionic dispersant its heat resistivity increases markedly with a minimal effect on the performance properties of the bulked clay pigment or the viscosity of the clay water slurry. Similar resistivity improvements in heat are obtained if this dispersion is spray dried and then redispersed in water. The following tests demonstrate how heat undesirably affects the viscosity of a slurry of bulked pigment containing a conventional dispersant. A clay-water slurry of (unbulked) feed clay (sodium silicate dispersed) was centrifuged to 62% solids. Solids were adjusted to 57%. The slurry was heated to 95°C. The slurry did not thicken. A bulking pigment was prepared by adding 0.08% Calgon 261 LV polymer (0.25% concentration) to a 20% solids slurry, followed by bleaching with sodium hydrosulfite bleach at pH 4.5, (adjusted with H₂SO₄) filtration, washing and dispersion with Mayo 148 D polyacrylate (a sodium polyacrylate compound, referred to as M148D hereafter) at 62% solids. This slurry was heated and it thickened at 60°C. The slurry thinned upon cooling but when it was reheated to 60°C, the slurry again thickened. This indicates that a chemical reaction was responsible for the undesirable thickening. The following tests were carried out to demonstrate the effectiveness of mixtures of polyacrylate and nonionic surfactant in improving heat resistance of dispersed slurries of the bulked pigment. DA 630 is a nonionic surfactant made by GAF Corporation and is reported to be decyloxy poly (ethyleneoxy) ethanol. CO 610 is also a nonionic surfactant made by GAF and is reported to be nonylphenoxy poly (ethyleneoxy) ethanol. The bulked pigment was prepared by adding 0.08% Calgon 261 LV polymer to a slurry of suitable kaolin clay feed. Sodium hydrosulfite bleach was added in amounts of 4-5 lb/ton of clay in the slurry at 4.5pH (adjusted with H₂SO₄) and the bleached slurry was filtered, washed and blunged with a mixture of dispersants. Brookfield viscosity was measured immediately and the heat resistance was tested the following day. The heat resistance test comprised heating the clay-water slurry at 62% solids in an open beaker on a hot plate with agitation, and observing its fluidity as a function of temperature. Results are reported below. Dispersant M148D/DA630 Brookfield Viscosity Heat Resistance 20RPM 100 RPM .15% / .15% 35 55 fluid at 92°C .175%/ .10% 55 67 fluid at 92°C .10% / .10% 50 65 fluid at 85°C .15% / .10% 60 69 fluid at boiling Various amounts of combinations of polyacrylate dispersant (Mayo 148 D) and nonionic surfactant (DA 630) were added to portions of washed filter cakes of kaolin bulked with Calgon 261 LV at the 0.08% level. The polyacrylate was first added during blunging followed by the nonionic surfactant. The results, shown below, demonstrate that mixtures of dispersants, when used at total levels above 0.175%, were effective in preventing thickening at temperatures above 60°C provided sufficient nonionic surfactant was present. Exp. Dispersant Viscosity Scattering Heat Effect; Thickens at Total M148D/DA630 Brookfield Hercules S₄₅₇ S₅₇₇ 20RPM 100RPM 1 .175% .114%/06% 90 97 16/705 .209 .151 45°C 2 .175% .0875%/.0875% 75 80 16/775 .202 .142 58°C 3 .175% .06%/.115% 10800 7280 16/225 .226 .168 Thick before heating (not tested) 4 .200% .13%/.07% 175 147 16/1020 .181 .125 48°C 5 .200% .1%/.1% 75 73 16/775 .160 .107 73°C 6 .200% .07%/.13% 120 110 16/425 .184 .127 45°C 7 .250% .1625%/.0875% 50 58 1.0/1100 .145 .097 90°C 8 .250% .125%/.125% 50 60 1.2/1100 .144 .096 90°C 9 .250% .0875%/.1625% 75 65 2.3/1100 .153 .102 87°C 10 .300% .195%/.105% 115 85 1.9/1100 .170 .118 83°C 11 .300% .15%/.15% 90 70 1.9/1100 .165 .115 91°C 12 .300% .105%/.195% 70 65 4.1/1100 .167 .114 93°C Also, various mixtures of polyacrylate (Mayo 148 D) dispersant and non-ionic surfactant (CO-610) were added to portions of washed filter cakes treated with .08% polymer (Calgon 261 LV) and bleached with 4.5 lb/ton sodium hydrosulfite. The results below show slight improvement in heat resistivity when slurries of these dispersed pigments at 62% solids were heated in a beaker on a hot plate while mixing. EXP Dispersant M148D - CO610 Brookfield Hercules Heat Effect; Thickens at 20RPM 100RPM 1 .1% - .05% 165 145 16/665 58°C 2 .15% - .05% 105 110 16/705 67°C 3 .2% - .05% 225 145 8/1100 60°C 4 .2% - .1% 105 100 16/995 63°C While specific components of the present system are defined above, many other variables may be introduced which may in any way affect, enhance or otherwise improve the system of the present invention. For example, the polyelectrolyte treated clay may be blended with other pigments having specific properties to produce coating colors. Examples of such pigments are high glossing kaolin clay or a delaminated kaolin clay. These are intended to be included herein. Although variations ore shown in the present application, many modifications and ramifications will occur to those skilled in the art upon reading of the present disclosure. For example, polyelectrolyte can be added to unbleached clay at an alkaline dispersion pH, at acid pH levels which are typically encountered in reductive bleaching, after the addition of the hydrosulfite and sulfuric acid bleaching reagents, to the repulped filter cake both in the presence or absence of deflocculating agents, etc. Furthermore, the use of diallyl homopolymers has been described. Those skilled in the art will recognize that the polymer can be modified by introducing other monomers during the polymerization so as to modify the diallyl ammonium polymer salt.

Claims: An aqueous slurry of chemically bulked hydrous kaolin clay pigment containing dispersant, characterized in that said slurry is heat stabilized by said dispersant comprising nonionic surfactant and polyacrylate salt dispersants, said nonionic surfactant being compatible with water and oil and has an HLB value of 3 to 18, said nonionic surfactant being present in an amount of from 0.05 to 0.3% based on the dry weight of the clay, and said polyacrylate salt being present in an amount of from 0.05 to 0.3% based on the dry weight of the clay. A slurry according to claim 1 wherein said pigment is obtained by flocculating a suspension of kaolin with cationic polyelectrolyte. A slurry according to claim 1 or 2 containing 60 dry wt.% solids or above. A slurry according to any preceding claim wherein said nonionic surfactant has an HLB value of 5 to 14. A slurry according to any preceding claim wherein said nonionic surfactant is present in an amount up to 0.15% of the weight of said clay. A slurry according to any preceding claim wherein said nonionic surfactant is selected from [a] decyloxypoly(ethyleneoxy) ethanols of formula C₁₀H₂₁O(C₂H₄O)nCH₂CH₂OH wherein n is an integer of 6 to 8, and [b] nonylphenoxypoly (ethyleneoxy) ethanols. A method for preparing an aqueous slurry of bulking pigment suitable for use in coating or filling paper which arises preparing a fluid aqueous suspension of particles of kaolin clay, adding thereto water-soluble cationic polyelectrolyte to thicken and flocculate said fluid suspension, acidifying the resulting flocculated clay suspension, bleaching the clay in said suspension with hydrosulfite salt, filtering said acidified suspension to recover bulked clay, washing the filtered clay and adding dispersant to the recovered bulked clay to provide a fluid suspension of bulked clay characterized in that said dispersant comprises nonionic surfactant and polyacrylate and improves the heat stability of said suspension, said nonionic surfactant being compatible with water and oil and having an HLB value of 3 to 18, said nonionic surfactant being present in an amount of from 0.05 to 0.3% based on the dry weight of the clay, and said polyacrylate salt being present in an amount of from 0.05 to 0.3% based on the dry weight of the clay. A method according to claim 7 wherein the amount of nonionic surfactant added is up to 0.15% of the weight of the clay. A method according to claim 7 or 8 wherein the nonionic surfactant has an HLB value of 5 to 14. A method according to claim 7, 8 or 9 wherein said nonionic surfactant is selected from [a] decyloxypoly(ethyleneoxy) ethanols of formula: C₁₀H₂₁O(C₂H₄O)nCH₂CH₂OH wherein n is an integer of 6 to 8, and [b] nonylphenoxypoly (ethyleneoxy) ethanols.

Inventors: NEMEH, SAAD, SLEPETYS, RICHARD A.
Applicants: ENGELHARD CORPORATION
Application year: 1987
Main classification: C09D17
IPC codes: B28C1, D21H19, C09D17, C09D1, C09C1, D21H17