The term"paper,"as used herein, includes sheet-like masses and molded products made from fibrous cellulosic material, which may be derived from natural sources, synthetics such as polyamides, polyesters, rayon and polyacrylic resins as well as from mineral fibers such as asbestos and glass.

In addition, paper made from combinations of cellulosic and synthetic materials are applicable herein. Paperboard is also included within the broad term"paper".

Papermaking, as it is conventionally known, is a process of introducing an aqueous slurry of pulp or wood cellulosic fibers (which have been beaten or refined to achieve a level of fiber hydration and to which a variety of functional additives can be added) onto a screen or similar device in such a manner that the water is removed, thereby forming a sheet of the consolidated fibers, which upon pressing and drying can be processed into dry roll or sheet form. Two well known papermaking processes involve the Fourdrinier machine, the most common, and the cylinder machine. In the Fourdrinier and multicylinder operations, and in other machine operations, as typical in papermaking, the feed or inlet to the machine is an aqueous slurry or water suspension of pulp fibers which is provided from what is called the

"wet end"system. In the wet end, the pulp along with other additives are mixed in an aqueous slurry and subject to mechanical and other operations such as beating and refining to improve interfiber bonding and other physical properties of the finished sheet. Additives commonly introduced along with the pulp fibers are pigments such as titanium dioxide, mineral fillers such as clay and calcium carbonate and other materials introduced into paper to achieve such properties as improved brightness, opacity, smoothness, ink receptivity, fire retardance, water resistance, increased bulk, etc.

It has been known to add various materials, including starch, to the pulp, or stock in the papermaking process or prior to the formation of the sheet, to aid in retention, drainage and strength properties.

Starch has been used in the paper industry for many years and, in fact, is the second largest volume raw material component in paper. Starches perform a number of functions in papermaking including strength improvement, increased drainage and increased retention of fibers, fines and other components on the wire. Both unmodified and modified types have been used.

Anionic and cationic starches as well as amphoteric starches have long been used as additives in papermaking for their contributions to strength and pigment retention in the paper. See, for example, U. S. Patent Nos.

3,459,632 issued to C. Caldwell et al. on August 5,1969 and 3,562,103 issued to K. Moser et al. on February 9,1971. More recent patents involving the use of starches in papermaking include U. S. Patent 4,876,336 issued to D. Solarek et al. on October 24,1989 which discloses the use of amphoteric starch derivatives and U. S. Patent 5,129,989 issued to S. Gosset et al. on

July 14,1992 which discloses the use of cationic and anionic starches in separate additions.

Despite the various and well known use of different starches in papermaking, there is the continuing need and desire to provide improved papermaking properties and especially improved retention.

SUMMARY OF THE INVENTION Now, it has been found that significantly improved retention properties can be obtained in the process of papermaking by the addition or combination of cationic starch and starch phosphate having a select zeta potential, to the stock or furnish in the wet end.

More particularly, this invention involves the process of making paper comprising adding to the paper stock or furnish prior to or during formation of the sheet, a combination of cationic starch and starch phosphate, the combination having a zeta potential of from about +20 to-18 mV (millivolts).

DETAILED DESCRIPTION OF THE INVENTION This invention involves a combination of modified cationic starches and starch phosphates in amounts to provide a selected zeta potential range for use in papermaking.

The modified starches which are used in this invention can be prepared by methods known and described in the art. Cationization of the starch can be produced by well known chemical reactions with reagents containing amino, imino, ammonium, sulfonium and phosphonium groups as disclosed, for example, in"Cationic Starches"by D. B. Solarek, Modified

Starches: Properties and Uses, Chapter 8, pp. 113-129,1986, and in U. S.

Patent No. 4,119,487 issued October 10,1978 to M. Tessler. Such cationic derivatives include those containing nitrogen groups comprising primary, secondary, tertiary and quaternary amines and sulfonium and phosphonium groups attached through either ether or ester linkages. The preferred derivatives are those containing the tertiary amino and quaternary ammonium ether groups.

The general method for preparing starches containing tertiary amine groups, which method involves reacting starch under alkaline conditions with a dialkylaminoalkyl halide is described in U. S. Patent No. 2,813,093 issued on November 12,1957 to C. Caldwell, et al. Another method, therefore, is disclosed in U. S. Patent No. 4,675,394 issued January 23,1987 to D. Solarek et al. The primary and secondary amine starches may be prepared by reacting the starch with aminoalkyl anhydrides, amino epoxides or halides, or the corresponding compounds containing aryl in addition to the alkyl groups.

Quaternary ammonium groups may be introduced into the starch by suitable treatment of the tertiary aminoalkyl ether or starch, as described in the previously noted U. S. Patent No. 2,813,093. Alternatively, quaternary groups may be introduced directly into the starch by treatment with the reaction product of an epihalohydrin and a tertiary amine or tertiary amine salt, to provide, for example, (3-timethylammonium chloride)-2-hydroxypropyl ether substituent groups as disclosed in the noted U. S. Patent No, 4,119,487.

The above noted patents, i. e.,'487,'093 and'394 are incorporated herein by reference.

The preparation of cationic sulfonium derivatives is described in U. S.

Patent No. 2,989,520 issued June, 1961 to M. Rutenberg et al. and essentially involves the reaction of starch in an aqueous alkaline medium with a beta-halo-genoalkylsulfonium salt, vinylsulfonium salt or epoxyalkylsulfonium salt. The preparation of cationic phosphonium derivatives is disclosed in U. S. Patent No. 3,077,469 issued February 12, 1963 to A. Aszalos and involves reaction of starch in an aqueous alkaline medium with a beta-halogenoalkylphosphonium salt.

Other suitable cationic starches may be provided using reagents and methods that are well known in the art as illustrated in the above references.

Further description of useful cationic starches are disclosed in U. S. Patent No. 2,876,217 issued March 3,1959 to E. Paschal, U. S. Patent No.

2,970,140 issued January 31,1961 to C. Hullinger et al., U. S. Patent No.

5,004,808 Issued April 2,1991 to M. Yalpani et al., U. S. Patent No. 5,093,159 issued March 3,1992 to J. Fernandez et al., and EP 406 837 published January 1,1991 (corresponding to U. S. Application Serial No. 516,024 filed April 26,1990), all of which are incorporated herein by reference. Particularly useful cationic derivatives are those containing amino or nitrogen groups having alkyl, aryl, aralkyl or cyclic substituents of up to 18 carbon atoms and especially alkyl of 1 to 6 carbon atoms.

The amount of cationic substituent on the starch can be varied and generally a degree of substitution (DS) of from about 0.003 to 0.2 and preferably from about 0.01 to 0.1 will be used. While larger amounts of cationic substituents or higher degrees of substitution (DS) could be used, they are more costly and difficult to make and therefore not economically

attractive. The term"degree of substitution" (DS) as used herein means the average number of sites or substituent groups per anhydroglucose unit of the starch molecule.

The anionic starch used in this invention is a starch phosphate monoester. The starch phosphate can be prepared by phosphorylation using any known method including the reaction with various inorganic phosphate salts. The preparation of starch phosphate monoesters using such methods are described in"Phosphorylated Starches and Miscellaneous Inorganic Esters"by D. B. Solarek, Modified Starches: Properties and Uses, Chapter 7, pp. 97-112,1986.

Phosphate groups are introduced into starch by thermal reaction with water-soluble ortho-, pyro-, meta-, or tripolyphosphates. Techniques for phosphorylating a starch base are further described in U. S. Patent Nos.

2,824,870 issued February 25,1959 to H. Neukom and 2,961,440 issued November 22,1960 to R. Kerr. These patents disclose techniques of heat reacting starch impregnated with a phosphate salt of an alkali metal, within a prescribed pH range. Previously noted U. S. Patent 3,562,103 directed to starches containing anionic phosphate groups, discloses a method of phosphorylating starch which comprises forming an aqueous starch slurry at room temperature and adding a suitable concentration of phosphate reagent.

Preferably, the pH is adjusted to between 4 and 6, although it is stated that a range of 4 to 11.5 may be used. The starch is filtered without washing and adjusted to a moisture level of about 20% or below, preferably from about 5 to 20% by weight at a temperature of less than about 70°C. The starch phosphate composition is then heated at a temperature of 100 to 160°C until

the product has the desired level of anionic phosphate groups. The above noted'870,'412,'440 and'103 patents are all incorporated herein by reference.

In U. S. Patent No. 4,166,173 issued August 28,1979 to O. B.

Wurzburg et al., which disclosure is incorporated herein by reference, starch is phosphorylated by an improved pollution-free process which involves forming a concentrated reagent solution of alkali metal tripolyphosphate salt and impregnating therewith a starch cake containing no more than 45% by weight of moisture. Drying and thermally reacting the thus impregnated starch provides the phosphorylated starch. In preparing the concentrated reagent solution during addition of the tripolyphosphate salt to the water, one or more acids are added to control the pH at between 2.8 and 5.0.

For the purpose of this invention, any phosphate containing starch, native or modified may be used. For the modified product, the phosphorylation may be carried out by any of the known techniques with the thermal reaction of the phosphate impregnated starch being performed at a pH between 5.5 and 8.5, and preferably 6.0 to 8.5. The reaction of starch is carried out with sodium or potassium tripolyphosphate, sodium or potassium hexametaphosphate and sodium or potassium pyrophosphate salts yielding orthophosphate mono-ester groups, i. e., mono-starch phosphates. Other alkali metal salts may be used in place of sodium or potassium which are preferred as the phosphorylating reagent.

Thus, in carrying out phosphorylations employing an aqueous starch slurry, the pH of the starch slurry containing the phosphorylating reagent is adjusted to about 5.5 to 8.5. Use of pH levels below about 5.5 will result in a

degraded starch while usu of pH levels above about 8.5 may produce undesirable crosslinking. If phosphorylation is to be carried out by spraying the reagent, a starch slurry is ordinarily prepared and adjusted to be within the designated pH range and is then filtered. The reagent is sprayed onto the pH adjusted starch cake. The practitioner will recognize that it is also possible to prepare the filter cake at a slightly alkaline pH and impregnate it with an acidic solution of phosphate reagent such that the final pH of the starch-phosphate reagent mixture is within the defined pH range. The specific reagent used may require adjustments of pH levels, For example, sodium tripolyphosphate (STP) has limited solubility in water (0.2 g/cc at 25°C). In order to achieve higher solids solutions, the pH is maintained at 4.0 to 6.0 by addition of acid such as HCI or H3PO4 during dissolution of the salt. In contrast, sodium hexametaphosphate (NaPO3) 6 shows very high solubility and concentrated solutions (20 to 36%, by weight) can be prepared with no pH adjustment.

Suitable starch phosphate for this invention will include about 0.03 to 1.0% bound phosphorus, preferably about 0.1 to 0.3%. By the term"bound phosphorus"we mean phosphorus which is attached by an ester linkage to a hydroxyl group of the anhydroglucose backbone of the derivatized starch.

Most commonly, the amount of phosphorylating reagent employed will range from about 0.5 to 12% by weight of dry starch. For example, treatment of waxy maize with 3.5 to 4.0% of sodium tripolyphosphate will give a starch containing 0.14 to 0.22% of bound phosphorus. The starch cake containing the phosphorylating reagent is dried to a moisture less than about 9.0% and preferably from about 2.0 to 7.0% prior to the required thermal treatment at higher temperatures. Ordinarily, the dry mixture of starch and

phosphorylating reagent is heated to temperatures of from about 110° to 140°C and preferably will range from about 130° to 135°C during the phosphorylation reaction. The heating period may range from 0.1 to 4 hours or more depending on the selected reagent, pH, temperature, etc.

The starch which may be used as the base material in preparing the modified cationic starch and anionic starch materials of this invention may be derived from any plant source including corn, potato, sweet potato, wheat, rice, waxy rice, tapioca, waxy maize, sago, sorghum, high amylose starch such as amylose corn having 40% or more of amylose content, etc. Starch flours may also be used. Also included are the conversion products derived from any of the former bases including, for example, dextrins prepared by the hydrolytic action of acid and/or heat; oxidized starches prepared by treatment with oxidants such as sodium hypochlorite ; fluidity or thin-boiling starches prepared by enzyme conversion or mild acid hydrolysis; derivatized or modified starches; and crosslinked starches. The starch base may be a granular starch or a gelatinized starch, i. e., non-granular starch. It is further noted that the starch base material may be the same or different for each of the cationic starch or anionic starch components.

While the amount of modification, i. e., the cationic substitution and anionic substitution on the respective starch components can vary as noted above, the essential feature of this invention is that the respective combinations of the two components are provided in proportions such that the net zeta potential of the starch combination will be in the range of from about +20 to-18 mV and preferably from about +15 to-5 mV. Keeping the zeta potential within this range is important because when using the starch

combination in a papermaking process, significant improvement is seen in filler retention as well as good drainage and strength properties.

When the papermaking process employing the cationic starch and anionic starch phosphate combination in accordance with this invention involves an alkaline papermaking system, i. e., where the pH of the system is typically greater than about 6.5, the starch combination will more particularly have a zeta potential of from about +18 to-18 mV and preferably from about +15 to-10 mV. When the papermaking process involves an acid papermaking system, i. e., pH of less than about 6.5, the cationic starch/anionic starch phosphate combination will have a zeta potential of from about +20 to +1 mV and preferably from about +17 to +5 mV.

The proportion or ratio of cationic starch and starch phosphate components in the starch combination of this invention can vary to a wide degree provided that the zeta potential range, as described herein, is satisfied. More particularly, the cationic starch and starch phosphate polymer components are generally provided in amounts of from about 4: 1 to 1: 4 parts by weight of cationic starch to starch phosphate. The term"zeta potential"as used herein refers to electrokinetic potential, the potential across the interface of solids and liquids and more particularly the potential across the diffuse layer of ions surrounding a charge colloidal particle. Zeta potential relates to surface charge and electrophoretic mobility and is a well known property measurement. A detailed discussion of zeta potential may be found in"Zeta Potential in Colloid Science, Principles and Applications"by Robert J. Hunter, Academic Press, 1988. Various methods are known for determining the zeta potential of different materials, with electrophoresis being the most common.

Electrokinetic phenomena are observed when two phases move relative to each other under the influence of an electric field. Electrophoresis describes the motion of charged particles or droplets in an applied electric field. A thin layer of liquid adheres to the particle or droplet surface so that the shearing plane is located anywhere in the liquid. The potential at the shearing plane is called the electrokinetic or zeta potential. Zeta potential can readily be measured by the technique of microelectrophoresis. This involves measuring the velocity of individual particles in suspension, viewed in a microscope fitted with a reticule, the transit times across the reticule being recorded. Several microelectrophoresis instruments are available for measuring zeta potential.

In this application, a Zetasizer 2000 instrument provided by Malvern Instruments Limited was used to measure zeta potential.

The combination of cationic starch and starch phosphate may be effectively used for addition to pulp prepared from any type of cellulosic fibers, synthetic fibers, or combinations thereof. Among the cellulosic materials which may be used are bleached and unbleached sulfate (kraft), bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite, semi- chemical, chemiground wood, ground wood or any combination of these fibers. Fibers of the viscose rayon or regenerated cellulose type may also be used if desired.

Any desired inert mineral fillers may be added to the pulp which is to be modified with the improved starch derivatives of this invention. Such materials include clay, titanium dioxide, talc, calcium carbonate, calcium sulfate and diatomaceous earths.

Other additives commonly introduced into paper may be added to the pulp or furnish, for example, dyes, pigments, sizing additives, alum, anionic retention aids, etc..

The amount of cationic starch and starch phosphate polymer combination (i. e. the total amount of both the cationic starch and starch phosphate components) that may be added to the wet end or paper pulp will be an effective additive amount, especially effective to improve filler retention.

More particularly, from about 0.05 to 10% of the starch combination and preferably from about 0.1 to 2% by weight, based on the dry weight of the furnish, may be used. The starch combinations is made as a component, i. e. the cationic starch and starch phosphate are combined together as one component to form the starch polymer combination. These starch materials or combination have to be dispersed or solubilized prior to addition to the papermaking system. This may be accomplished by standard or known techniques such as batch cooking, jet cooking or steam injection cooking.

The starch components can either be cooked together as a blend or cooked separately, then blended and combined together and added as one component to the papermaking system.

In addition to the selected starch derivatives and other components that may be included in the alkaline papermaking system as described above, colloidal inorganic minerals may be added to the system to form an alkaline microparticle system. Such microparticle systems include colloidal silica, bentonite and anionic alum and may be incorporated into the system in amounts of at least 0.001% and more particularly from about 0.01 to 1% by weight based on the weight of dry pulp. Further description of such

microparticle inorganic materials may be found In U. S. Patent No. 4,388,150 issued June 14,1983; U. S. Patent No. 4,643,801 issued February 17,1987; U. S. Patent No. 4,753,710 issued June 28,1988 and U. S. Patent No.

4,913,775 issued April 3,1990; all of which are incorporated herein by reference.

The following examples will further illustrate the embodiments of this invention. In these examples all parts are given by weight and all temperatures in degrees Celsius unless otherwise noted.

EXAMPLE I A cationic starch was prepared in the following manner. Waxy maize (2500 g, about 10% moisture) and 3750 ml of water were charged into reactor vessel fitted with means for heating and mechanical agitation. Under agitation, the slurry temperature was raised to 43°C and the pH adjusted to 11.2 to 11.5 using an aqueous solution of sodium hydroxide (4% by weight).

With agitation, 208 g of a 60% active, aqueous solution of 3-chloro-2- hydroxypropyltrimethyl ammonium chloride were added and the mixture allowed to react at 43°C for 24 hours. The final pH of the system was 11.6.

After the reaction was completed, the slurry was neutralized to pH of 7.0 with 10% hydrochloric acid and filtered. The cake was washed with water and air- dried at room temperature. It was found to have a nitrogen content of 0.32% by weight on a dry basis (db).

An anionic starch phosphate was prepared as follows. Waxy maize (400 g) with pH adjusted to 8.5 was placed in a Hobart mixer and impregnated with an aqueous solution of sodium tripolyphosphate (STP) (9.5,

g STP, 25.8 g H2O) to provide a treatment level of 2.3%. The pH of the resulting slurry was adjusted to 5.3 with the slow addition of HCI to get complete dissolution. The STP solution was applied to the starch via a manual spray bottle over about 5 minutes. After STP addition was complete, mixing was continued for 10 minutes. The resulting impregnated starch was dried at 60°C to 4% moisture in a forced air oven. The resulting material was ground to a fine powder, spread as a thin layer on a tray, and heated to 155°C for 30 minutes in a forced air oven. The amount of bound phosphorus in the product was determined by washing the sample with a 5% aqueous solution of ethylenediamine tetraacetic acid (EDTA) followed by rinsing with distilled water and measuring the phosphorus by inductively couple plasma (ICP) after acid dissolution of the starch. The sample product was found to have a bound phosphorus of 0.19%. Similar products were made using tapioca and corn based starches.

Various combinations of the above prepared cationic starch and starch phosphate were made having different zeta potential charges (mV).

The zeta potentials were determined using a Zetasizer 2000 instrument obtained from the Malvern Instruments Limited. Using this instrument, which involves a microelectrophoresis technique, and the procedure recommended by the manufacturer, zeta potential measurements were made for the various combinations. Sample combinations were prepared by dispersing 1 g of the selected starch combination in distilled water in a 150 mi Pyrex beaker. The dispersed combination was cooked in boiling water for 30 minutes, with stirring for the first 5 minutes. The combination was diluted to 0.1% with distilled water and cooled to room temperature. Samples of the starch

combination solutions (20 cc) were injected into the instrument set at 25°C, and the average of three zeta potential readings recorded.

The various combinations were evaluated for filler retention in both alkaline and acid papermaking systems using standard Dynamic Alkaline Retention Evaluation, Tappi T 261 pm 90.

A standard papermaking furnish was prepared using a pulp stock which comprised an aqueous slurry of bleached hardwood kraft pulp (BHWK) and bleached softwood kraft pulp (BSWK). The pulp stock (80: 20 BHWK: BSWK, parts by weight) was refined in a standard laboratory Valley beater to about 400 CSF (Canadian Standard Freeness) and a pH of 7.8 to 8.2 and contained precipitated calcium carbonate filler (30% db) with 8 to 10% fiber fines and total fines of 37 to 42%.

The test was run while mixing and agitating using a Britt Jar with a screen having holes 76 microns in diameter. Sample combinations in various proportions with different zeta potentials were evaluated by adding selected amounts of the combinations to the pulp stock. The percent CaCO3 retention was determined for each sample with the results given below in Table 1.

Similar results were obtained using an acid papermaking system with the filler clay retention results also given in Table 1.

A review of this table and the retention results will indicate that significant retention property improvements are obtained when using combinations of cationic starch and starch phosphate having zeta potential values within the selected range as described in this application.

TABLE ! Acid papermaking (pH-6. 0)-Percent Clay Retention Cationic/Anionic Zeta Amounts Applied Starch Combinations Potential (mV) (% on wt. of furnish) <BR> <BR> (w/w)<BR> 0. 5 1. 0 1. 5 2. 0 100/0 +24.5 24.5 24.6 23.4 24.7 80/20 +21.1 28.6 31.5 32.3 33.7 70/30 +17.6 30.9 37.5 40.4 41. 7 60/40 +15.8 30.2 38.1 45.6 49.7 50/50 +13.3 27.1 38.2 44 52.9 40/60 +1.1 19.4 22.8 27.9 34.6 30/70-7.8 19.4 24.4 27.9 36.8 20/80-16.4 18.9 20.9 25.3 28.8 0/100-19. 7 17.2 16.8 16.9 17.0 Alkaline Papermaking (pH-7. 8)-Percent CaC03 Retention Cationic/Anionic Zeta Amounts Applied Starch Combinations Potential (mV) (% on wt. of furnish) (w/w) 0. 5 1. 0 1. 5 2. 0 100/0 +24.5 11.3 8.2 8.4 8.5 80/20 +21.1 17.2 17.1 16.1 15.9 70/30 +17.6 19.4 19.7 19.4 18.7 60/40 +15. 8 20.2 21.6 20.9 20 50/50 +13.3 23.2 25.2 26.3 26.5 40/60 +1.1 27.2 32.1 32.2 33 30/70-7.8 23.7 26.6 27.5 29.4 20/80-16. 4 20.9 22.9 24.1 26.2 0/100-19.7 18.4 18.4 18.8 17.2 EXAMPLE 2 For comparative purposes, sample combinations of cationic starch and starch phosphates as prepared in Example I and having zeta potential within the preferred ranges were evaluated for calcium carbonate retention and compared with an amphoteric waxy starch material (0.25% cationic N

content, 0.12% bound P content) and a cationic waxy starch (0.33% N quat).

Results are reported in Table 2 below.

Similar results are given for the same starch combinations in an acid system to determine percent filler clay retention. Results are also found in Table 2.

The results show the significantly improved retention properties in both alkaline and acid papermaking systems when using the starch combinations of this invention when compared to an amphoteric starch (having both cationic and anionic groups on the same starch molecule) or a cationic starch.

TABLE 2 Alkaline Papermaking System Amount Applied (% on wt. of furnish) Samples Zeta Potental (mV) _ 1. 0 1. 5 2. 0 Cationic/Anionic Starch +13.3 17.1 18.8 19.6 18.3 50/50 Combination Cationic/Anionic Starch +1.1 20.6 20.8 21.5 22.5 40/60 Combination Control (Amphoteric Starch) +14.8 12.6 11.1 10.4 9.2 Control (Cationic Starch) +24.5 9.2 6.3 5 5.6 Acid Papermaking System Amount Applied (% on wt. of furnish) Samples Zeta Potental (mV) CL5 5 1. 0 1. 5 2. 0 Cationic/Anionic Starch +13.3 44.1 49.3 50.1 47.6 50/50 Combination Cationic/Anionic Starch +1.1 44.6 49.5 48.8 47.6 40/60 Combination Control (Amphoteric Starch) +14.8 35.6 36.7 35 33.3 Control (Cationic Starch) +24.5 27.4 25.6 24.7 26.5

EXAMPLE 3 Additional combinations of cationic starch and starch phosphates were prepared as in Example 1 using tapioca starch as the base material.

The cationic tapioca had a nitrogen content of 0.24% (db) and the tapioca phosphate had a bound phosphorus of 0.18%. Combinations of the tapioca starches were made having zeta potentials within the desired range and evaluated for calcium carbonate retention in an alkaline papermaking system and for clay retention in an acid papermaking system. The results are shown in Table 3 below and are compared with an amphoteric tapioca starch (0.28% cationic N; 0.1 % bound P) and a cationic tapioca starch (0.24% cationic N).

The results in Table 3 show significant improvement in retention in both alkaline and acid papermaking systems when using the starch combinations of this invention when compared to the amphoteric tapioca (having both cationic and phosphate groups on the same starch molecule) or a cationic tapioca starch.

TABLE 3 Acid Papermaking (pH 6.0)-Clay Retention (%) Amount Applied (% on wt. of furnish) Samples Zeta Potential (mV) 0. 5 1. 0 1. 5 2. 0 Cationic/Anionic Tapioca +13. 8 48.5 54.7 56.9 56.6 (50/50-w/w Combination) Cationic/Anionic Tapioca-4.9 46.4 56.5 61.3 63. 9 (40/60-w/w Combination) Amphoteric Tapioca (Control) +22. 5 34.2 33.7 32.3 32.2 Cationic Tapioca (Control) +28. 7 28.6 28.6 30.4 29.6

Alkaline Papermaking (pH 7.8)-CaCOg Retention (%) Amount Applied (% on wt. of furnish) Samples Zeta Potential (mV) 0. 5 1. 0 1. 5 2. 0 Cationic/Anionic Tapioca 21.1 21.5 21.4 20.8 (50/50-w/w Combination) Cationic/Anionic Tapioca 22 22.2 24.3 23.8 (40/60-w/w Combination) Amphoteric Tapioca (Control) 14.7 13.3 11.6 11.6 Cationic Tapioca (Control) 10.4 8.3 8.4 9.6 EXAMPLE 4 Samples of cationic starch and starch phosphate were prepared as in Example 1 with the individual starches cooked separately and then combinded together before adding to the papermaking system. Starch combinations were evaluated as a 50/50, weight/weight (w/w) sample for CaCO3 retention in an alkaline papermaking system. Results are compared with an amphoteric starch and a cationic starch (all starches are the same as in Example 1) and given below in Table 4. These results show the improved retention properties for the starch combinations of this invention when compared to either the amphoteric or cationic starches.

TABLE 4 Alkaline Papermaking (pH 7. 8)-CaCO3 Retention (%) Amount Applied (% on wt. of furnish)

Samples Zeta Potential (mV) 0. 5 1. 0 1. 5 2. 0 Cationic/Starch Phosphate 15.3 23.4 26.9 28.1 32.4 (50/50-w/w Combination) Amphoteric Starch (Control)) 13.7 23.5 22.8 20.3 20.3 Cationic Starch (Control) 25.3 17.5 14.8 10.8 12.8