Charged organic polymer microbeads in paper making process

Abstract: In a papermaking process, improved drainage and retention are obtained when ionic, organic microbeads of less than about 1,000 nm in diameter if crosslinked or less about than 60 nm in diameter if noncrosslinked are added either alone or in combination with a high molecular weight organic polymer, and/or polysaccharide. Further addition of alum enhances drainage formation and retention properties in papermaking stock with and without the present of other additives used in papermaking processes.

Description: The present invention relates to a method of making paper comprising adding to an aqueous paper furnish charged organic microbeads. The invention also relates to a composition comprising the microbeads. In the past decade, the concept of using colloidal silica and bentonite to improve drainage, formation and retention has been introduced to papermaking. Fast drainage and greater retention of fines contribute to lower cost in papermaking and improvements are always being sought. U.S. -A-4,388,150 and 4,385,961 disclose the use of a two-component binder system comprising a cationic starch and an anionic, colloidal, silicic acid sol as a retention aid when combined with cellulose fibers in a stock from which it is made. Finnish Published Specification Nos. 67,735 and 67,736 refer to cationic polymer retention agent compounds including cationic starch and polyacrylamide as useful in combination with an anionic silica to improve sizing. U.S. -A-4,798,653 discloses the use of cationic colloidal silica sol with an anionic copolymer of acrylic acid and acrylamide to render the paper stock resistant to destruction of its retention and dewatering properties by shear forces in the paper-making process. A coacervate binder, three component system composed of a cationic starch, an anionic high molecular weight polymer and dispersed silica having a particle diameter range from 1 to 50 nm is revealed in U.S. -A-4,643,801 and 4,750,974. The above Finish publications also disclose the use of bentonite with cationic starch and polyacrylamides. U.S. -A- 4,305,781 discloses a bentonite-type clay in combination with high molecular weight, substantially non-ionic polymers such as polyethylene oxides and polyacrylamide as a retention aid. Later, in U.S. -A- 4,753,710, bentonite and a substantially linear, cationic polymer such as cationic acrylic polymers, polyethylene imine, polyamine epichlorohydrin, and diallyl dimethyl ammonium chloride are claimed to give an improved combination of retention, drainage, drying and formation. It is noted that the silica sol and bentonite are inorganic microparticle materials. Latices of organic microparticles have been ; used in high concentrations of 13.6 - 31.7 kg/907 kg (30-70 lbs/ton) to give "high-strength" paper products such as gasket materials, roofing felt, paperboard and floor felt and in paper with 30-70% mineral fillers (U.S. -A- 4,445,970). It is stated that latices have not been used in fine papermaking because such latices are sticky and difficult to use on a Fourdrinier machine. The latices of the above and following four patent references were made according to U.S. -A- 4,056,501. They are all emulsions of polymers made from styrene, butadiene and vinylbenzyl chloride which polymers are reacted with trimethylamine or dimethyl sulfide to produce an "onium" cation which is called a pH independent structured latex of 50 to 1000 nm in diameter. These structured cationic latices are used at high levels of concentration i.e. 13.6 - 90.7 kg/907 kg (30-200 lbs/ton) with an anionic, high molecular weight polymer, (U.S. -A- 4,187,142) or with an anionic polymer (U.S. -A- 4,189,345) or as both cationic and anionic latices (U.S. -A- 4,225,383). These latices are preferably from 60-300 nm in size. It has been found, in accordance with the present invention, that noncrosslinked organic microbeads of this size and larger are not effective. Furthermore, the process of the present invention uses organic microbeads at a level of 0.02 to 9.07 kg/907 kg (0.05 to 20 lbs/ton), preferably 0.04 to 3.4 kg/907 kg (0.10 to 7.5 lbs/ton) whereas the microbeads of the preceding five U.S. Patents are used at 13.6 - 90.7 kg/907 kg (30-200 lbs/ton) to give strength to paper products such as gaskets with a very high 30-70% mineral content. This prior art does not contemplate the use of charged organic micro-beads as a drainage and retention aid at the very low levels as required by the present invention. The use of an organic crosslinked microbead, in papermaking is taught in Japanese Patent Tokkai JP235596/63:1988 and Kami Pulp Gijitsu Times, pgs 1-5, March 1989 as a dual system of a cationic or anionic organic microbead of 1-100 µm and an anionic, cationic or nonionic acrylamide polymer. The waterswelling type, cationic, polymer particle is a crosslinked homopolymer of 2-methacryloyloxyethyl trimethylammonium chloride or a crosslinked copolymer of 2-methacryloyloxy-ethyl trimethylammonium chloride/acrylamide (60/40 weight percent). The acrylamide polymer is an acrylamide homopolymer or acrylamide hydroylsate of 17 mole percent anion-conversion or a copolymer of acrylamide/2-methacryloyloxyethyl trimethylammoniumchloride (75/25 weight percent). The anionic microbead is an acrylamide-acrylic acid copolymer. EP-A-0273605 teaches the addition of microbeads having a diameter ranging from about 49-87 nm and produced from terpolymers of vinyl acetate (84.6), ethyl acrylate (65.4) and acrylic acid (4.5) or methacrylonitrile (85), butyl acrylate (65) and acrylic acid (3). These polymeric beads are disclosed as added to an LBKP pulp slurry in order to evaluate the resultant paper for sizing degree, paper force enhancement and disintegratability. These polymer beads fall outside the scope of those used in the present invention in that the ionic content thereof is too small to impart any appreciable improvement in retention and drainage in the papermaking process. The present invention encompasses crosslinked, ionic, organic, polymeric microbeads having an unswollen particle diameter of less than about 750 nm or microbeads of less than about 60 nm if noncrosslinked and water-insoluble, as a retention and drainage aid, their use in papermaking processes, and compositions thereof with high molecular weight polymers and/or polysaccharides. EP-A-0,202,780 describes the preparation of crosslinked, cationic, polyacrylamide beads by conventional inverse emulsion polymerization techniques. Crosslinking is accomplished by the incorporation of difunctional monomer, such as methylenebisacrylamide, into the polymer chain. This crosslinking technology is well known in the art. The patent teaches that the crosslinked beads are useful as flocculants but are more highly efficient after having been subjected to unusual levels of shearing action in order to render them water-soluble. US-A- 4178205 describes a method for preparing a non-woven fibrous web. The method comprises (a) mixing an aqueous slurry of a negatively charged, water-insoluble, natural or synthetic fiber or a blend of such fibers with a structured particle latex having particles consisting of a non-ionic organic polymer core encapsulated by a thin polymer layer having bound charges of pH independent cationic groups, said charges being present in an amount of from about 0.15 milliequivalent to about 0.6 milliequivalent per gram of polymer in the latex; the non-ionic polymer core having a glass transition temperature of from about -80°C. to about 100°C.; the amount of said latex being not greater than the amount required to cause charge reversal on the fiber; (b) draining water from the aqueous suspension to form a wet web; (c) wet pressing the web; and (d) heating the wet web; whereby there is formed a non-woven fibrous web having polymer uniformly distributed and bonded to the fiber. The fiber can be a paper making pulp and the product may be a paper. EP-A-315718 describes an aqueous dispersion of a cationic polymer obtained by reacting an ethylene copolymer comprising from 40 to 80% by weight of ethylene and from 20 to 60% by weight of at least one aminoalkyl acrylamide comonomer represented by formula wherein R represents a hydrogen atom or a methyl group; R 2 and R 3 each represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms: and n represents an integer of from 2 to 4 and optionally up to 20 wt% of a comonomer and having a melt index as measured in accordance with JIS K-6760 of from 10 to 1,000 g/10 min. with hydrochloric acid in water to form a quaternary salt and subsequently reacting the resulting quaternary salt with an epihalohydrin compound through addition reaction. The cationic polymer can be added to a pulp slurry to obtain paper. US-A-4659431 discloses cationic sizing agents for paper. They can be obtained by a method in which a water-soluble cationic chemically pure terpolymer compound consisting of (a) 7-40% by weight of N, N-dimethylaminoethyl acrylate and/or methacrylate, (b) 40-80% by weight of styrene and (c) 4-40% by weight of acrylonitrile is dissolved in an aqueous medium, the sum of the components (a) to (c) always being 100% by weight and at least 10% of the N, N-dimethylamino groups of the terpolymer being quaternized and the remainder being protonated, and, in the presence of 10 to 70% by weight, relative to the monomer mixture below, of this emulsifier, (d) 0 to 90% by weight of acrylonitrile and/or methacrylonitrile, (e) 5 to 95% by weight of styrene and (f) 5 to 95% by weight of acrylates and/or methacrylates having 1 to 12 C atoms in the alcohol radical, the sum of the components (d) to (f) always being 100% by weight, are emulsified, and the emulsion thus obtained is subjected to free radical-initiated emulsion polymerization at temperatures from 20° to 150°C. Typically, the particle size of polymers prepared by conventional, inverse, water-in-oil, emulsion, polymerization processes are limited to the range of 1-5 µm since no particular advantage in reducing the particle size has hitherto been apparent. The particle size which is achievable in inverse emulsions is determined by the concentration and activity of the surfactant(s) employed and these are customarily chosen on the basis of emulsion stability and economic factors. The present invention is directed to the use, in papermaking, of cationic and anionic, crosslinked, polymeric, microbeads. Microgels are made by standard techniques and microlatices are purchased commercially. The polymer microbeads are also prepared by the optimal use of a variety of high activity surfactant or surfactant mixtures to achieve submicrometer size. The type and concentration of surfactant should be chosen to yield particles having an unswollen particle diameter of less than about 750 nm and more preferably less than about 300 nm. According to the present invention, there is provided a method of making paper from an aqueous suspension of cellulosic papermaking fibers, whereby improved drainage, retention and formation properties are achieved. The method comprises adding to the suspension, from about 0.02 to about 9.07 kg/907 kg (about 0.05 to 20 lbs/ton) of an ionic, organic polymer microbead having an unswollen particle diameter of less than about 750 nanometers if crosslinked or of less than about 60 nm if noncrosslinked and insoluble. Additionally, from about 0.02 to about 9.07 kg/907 kg (about 0.05 to about 20 lbs/ton), preferably about 0.04 to about 2.26 kg/907 kg (about 0.1 - 5.0 lbs/ton), of a high molecular weight, hydrophilic ionic organic polymer, and/or from about 0.45 to about 22.68 kg (about 1.0 to about 50.0), preferably about 2.27 to 13.6 kg/907 kg (about 5.0 - 30.0 lbs/ton) of an ionic polysaccharide, such as starch, preferably of a charge opposite that of the microbead, may be used. The synthetic organic polymer and polysaccharide may also be of opposite charge to each other. The addition of the microbead compositions results in significant increase in fiber retention and improvement in drainage and formation, said kg/907 kg (lbs/ton) being based on the dry weight of the paper furnish solids. The organic polymer microbeads may be either cationic or anionic. Alum or any other active, soluble aluminum species such as polyhydroxyaluminum chloride and/or sulfate and mixtures thereof have been found to enhance drainage rates and retention if they are incorporated into the furnish when used with the microbead compositions 0.04 to 9.07 kg/907 kg (0.1 to 20 lbs/ton), as alumina, based on the dry weight of paper furnish solids, are exemplary. The microbeads may be made as microemulsions by a process employing an aqueous solution comprising a cationic or anionic monomer and crosslinking agent; an oil comprising a saturated hydrocarbon; and an effective amount of a surfactant sufficient to produce particles of less than about 0.75 µm in unswollen number average particle size diameter. Microbeads are also made as microgels by procedures described by Ying Huang et. al., Makromol. Chem. 186, 273-281 (1985) or may be obtained commercially as microlatices. The term "microbead", as used herein, is meant to include all of these configurations, i.e. beads per se, microgels and microlatices. Polymerization of the emulsion may be carried out by adding a polymerization initiator, or by subjecting the emulsion to ultraviolet irradiation. An effective amount of a chain transfer agent may be added to the aqueous solution of the emulsion, so as to control the polymerization. It was surprisingly found that the crosslinked, organic, polymeric microbeads have a high efficiency as retention and drainage aids when their particle diameter is less than about 750 nm in the unswollen state and preferably less than about 300 nm, and that the noncrosslinked, organic, water-insoluble polymer microbeads have a high efficiency when their size is less than about 60 nm. The efficiency of the crosslinked microbeads at a larger size than the noncrosslinked microbeads may be attributed to the small strands or tails that protrude from the main crosslinked polymer. Using the ionic, organic, crosslinked, polymeric microbeads having an unswollen particle diameter of less than about 750 nm or the noncrosslinked, water-insoluble beads having an unswollen particle diameter of less than about 60 nm according to this invention, improved drainage, formation and greater fines and filler retention values are obtained in papermaking processes. These additives may be added, alone or in conjunction with other materials, as discussed below, to a conventional paper making stock such as traditional chemical pulps, for instance, bleached and unbleached sulphate or sulphite pulp, mechanical pulp such as groundwood, thermomechanical or chemi-thermomechanical pulp or recycled pulp such as deinked waste and any mixtures thereof. The stock, and the final paper, can be substantially unfilled or filled, with amounts of up to about 50%, based on the dry weight of the stock, or up to about 40%, based on dry weight of paper of filler, being exemplary. When filler is used any conventional filler such as calcium carbonate, clay, titanium dioxide or talc or a combination may be present. The filler, if present, may be incorporated into the stock before or after addition of the microbeads. Other standard paper-making additives such as rosin sizing, synthetic sizings such as alkyl succinic anhydride and alkyl ketene dimer, alum, strength additives, promoters, polymeric coagulants such as low molecular weight polymers, dye fixatives, etc. and other materials that are desirable in the papermaking process, may also be added. The order of addition, specific addition points, and furnish modification itself are not critical and normally will be based on practicality and performace for each specific application, as is common papermaking practise. When using cationic, high molecular weight polymer(s), or polysaccharides, and anionic microbeads, the preferred sequence of addition is cationic, high molecular weight polymer and then anionic bead. However, in some cases the reverse may be used. When a cationic polysaccharide such as starch and a cationic polymer are both used, they can be added separately or together, and in any order. Furthermore, their individual addition may be at more than one point. The anionic microbeads may be added before any cationic components or after them with the latter being the preferred method. Split addition may also be practised. Preferred practise is to add cationic polysaccharide before high molecular weight cationic polymer. The furnish may already have cationic starch, alum, cationic (or anionic or both cationic and anionic) polymers of molecular weight equal or less than 100,000, sodium aluminate, and basic aluminum salts (e.g., polyaluminum chloride and/or sulfate) and their levels may be varied to improve the response of the furnish, as discussed above. Addition points are those typically used with dual retention & drainage systems (pre-fan pump or pre-screen for one component and pre- or post-screens for another). However, adding the last component before the fan pump may be warranted in some cases. Other addition points that are practical can be used if better performance or convenience is obtained. Thick stock addition of one component is also possible, although thin stock addition is preferred. However, thick stock and/or split thick and thin stock addition of cationic starch is routinely practised and these addition modes are applicable with the use of the microbead as well. Addition points will be determined by practicality and by the possible need to put more or less shear on the treated system to ensure good formation. When using high molecular weight, anionic polymer(s) and cationic microbeads, the preferred sequence is anionic polymer and then cationic beads, although in some cases the reverse may be used. When anionic polymer and anionic polysaccharide are both used, they can be added separately or together, and in any order. The microbeads may also be used in combination with high molecular weight ionic polymers of similar or opposite charge. The microbeads are crosslinked, cationic or anionic, polymeric, organic microparticles having an unswollen number average particle size diameter of less than about 750 nanometers and a crosslinking agent content of above about 4 molar parts per million based on the monomeric units present in the polymer and are generally formed by the polymerization of at least one ethylenically unsaturated cationic or anionic monomer and, optionally, at least one non-ionic comonomer in the presence of said crosslinking agent. They preferably have a solution viscosity (SV) of about 1.1-2.0 mPa.s. Cationic microbeads used herein include those made by polymerizing such monomers as diallyldialkylaznmoniun halides; acryloxyalkyltrimethylammonium chloride; (meth)acrylates of dialkylaminoalkyl compounds, and salts and quaternaries thereof and, monomers of N,N-dialkylaminoalkyl(meth)acrylamides, acrylamides, and salt and quaternaries thereof, such as N,N-dimethyl aminoethylacrylamides; (meth)acrylamidopropyltrimethylammonium chloride and the acid or quaternary salts of N,N-dimethylaminoethylacrylate and the like. Cationic monomers which may be used herein are of the following general formulae: where R 1 is hydrogen or methyl, R 2 is hydrogen or lower alkyl of C 1 to C 4 , R 3 and/or R 4 are hydrogen, alkyl of C 1 to C 12 , aryl, or hydroxyethyl and R 2 and R 3 or R 2 and R 4 can combined to form a cyclic ring containing one or more hetero atoms, Z is the conjugate base of an acid, X is oxygen or -NR 1 wherein R 1 is as defined above, and A is an alkylene group of C 1 to C 12 ; or where R 5 and R 6 are hydrogen or methyl, R 7 is hydrogen or alkyl of C 1 to C 12 and R 8 is hydrogen, alkyl of C 1 to C 12 , benzyl or hydroxyethyl; and Z is as defined above. Anionic microbeads that are useful herein those made by hydrolyzing acrylamide polymer microbeads etc. those made by polymerizing such monomers as (methyl)acrylic acid and their salts, 2-acrylamido-2-methylpropane sulfonate, sulfoethyl- (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid, maleic or other dibasic acids or their salts or mixtures thereof. Nonionic monomers, suitable for making microbeads as copolymers with the above anionic and cationic monomers, or mixtures thereof, include (meth)acrylamide; N-alkyacrylamides, such as N-methylacrylamide; N,N-dialkylacrylamides, such as N,N-dimethylacrylamide; methyl acrylate; methyl methacrylate; acrylonitrile; N-vinyl methylacetamide; N-vinyl methyl formamide; vinyl acetate; N-vinyl pyrrolidone, mixtures of any of the foregoing and the like. These ethylenically unsaturated, non-ionic monomers may be copolymerized, as mentioned above, to produce cationic, anionic or amphoteric copolymers. Preferably, acrylamide is copolymerized with an ionic and/or cationic monomer. Cationic or anionic copolymers useful in making microbeads comprise from about 0 to about 99 parts, by weight, of non-ionic monomer and from about 100 to about 1 part, by weight, of cationic or anionic monomer, based on the total weight of the anionic or cationic and non-ionic monomers, preferably from about 10 to about 90 parts, by weight, of non-ionic monomer and about 10 to about 90 parts, by weight, of cationic or anionic monomer, same basis i.e. the total ionic charge in the microbead must be greater than about 1%. Mixtures of polymeric microbeads may also be used if the total ionic charge of the mixture is also over about 1%. If the anionic microbead is used alone, i.e. in the absence of high molecular weight polymer or polysaccharide, in the process of the present invention, the total anionic charge thereof must be at least about 5%. Most preferably, the microbeads contain from about 20 to 80 parts, by weight, of non-ionic monomer and about 80 to about 20 parts by weight, same basis, of cationic or anionic monomer or mixture thereof. Polymerization of the monomers occurs in the presence of a polyfunctional crosslinking agent to form the cross-linked microbead. Useful polyfunctional crosslinking agents comprise compounds having either at least two double bounds, a double bond and a reactive group, or two reactive groups. Illustrative of those containing at least two double bounds are N,N-methylenebisacrylamide; N,N-methylenebismethacrylamide; polyethyleneglycol diacrylate; polyethyleneglycol dimethacrylate; N-vinyl acrylamide; divinylbenzene; triallylommonium salts, N-methylallylacrylamide and the like. Polyfunctional branching agents containing at least one double bond and at least one reactive group include glycidyl acrylate; glycidyl methacrylate; acrolein; methylolacrylamide and the like. Polyfunctional branching agents containing at least two reactive groups include dialdehydes, such as gyloxal; diepoxy compounds; epichlorohydrin and the like. Crosslinking agents are to be used in sufficient quantities to assure a cross-linked composition. Preferably, at least about 4 molar parts per million of crosslinking agent based on the monomeric units present in the polymer are employed to induce sufficient crosslinking and especially preferred is a crosslinking agent content of from about 4 to about 6000 molar parts per million, most preferably, about 20-4000. The polymeric microbeads of this invention are preferably prepared by polymerization of the monomers in an emulsion. Polymerization in microemulsions and inverse emulsions may be used as is known to those skilled in this art. P. Speiser reported in 1976 and 1977 a process for making spherical "nanoparticles" with diameters less than 80 nm (800 Å) by (1) solubilizing monomers, such as acrylamide and methylenebisacrylamide, in micelles and (2) polymerizing the monomers, See J. Pharm. Sa., 65(12), 1763 (1976) and US-A- 4,021,364. Both inverse water-in-oil and oil-in-water "nanoparticles" were prepared by this process. While not specifically called microemulsion polymerization by the author, this process does contain all the features which are currently used to define microemulsion polymerization. These reports also constitute the first examples of polymerization of acrylamide in a microemulsion. Since then, numerous publications reporting polymerization of hydrophobic monomers in the oil phase of microemulsions have appeared. See, for examples, U.S. -A- 4,521,317 and 4,681,912; Stoffer and Bone, J. Dispersion Sci. and Tech., 1(1), 37, 1980; and Atik and Thomas , J. Am. Chem. Soc., 103 (14), 4279 (1981); and GB-A-2161492. The cationic and/or anionic emulsion polymerization process is conducted by (i) preparing a monomer emulsion by adding an aqueous solution of the monomers to a hydrocarbon liquid containing appropriate surfactant or surfactant mixture to form an inverse monomer emulsion consisting of small aqueous droplets which, when polymerized, result in polymer particles of less than 0.75 µm in size, dispersed in the continuous oil phase and (ii) subjecting the monomer microemulsion to free radical polymerization. The aqueous phase comprises an aqueous mixture of the cationic and/or anionic monomers and optionally, a non-ionic monomer and the crosslinking agent, as discussed above. The aqueous monomer mixture may also comprise such conventional additives as are desired. For example, the mixture may contain chelating agents to remove polymerization inhibitors, pH adjusters, initiators and other conventional additives. Essential to the formation of the emulsion, which may be defined as a swollen, transparent and thermodynamically stable emulsion comprising two liquids insoluble in each other and a surfactant, in which the micelles are less than 0.75 µm in diameter, is the selection of appropriate organic phase and surfactant. The selection of the organic phase has a substantial effect on the minimum surfactant concentration necessary to obtain the inverse emulsion. The organic phase may comprise a hydrocarbon or hydrocarbon mixture. Saturated hydrocarbons or mixtures thereof are the most suitable in order to obtain inexpensive formulations. Typically, the organic phase will comprise benzene, toluene, fuel oil, kerosene, odorless mineral spirits or mixtures of any of the foregoing. The ratio, by weight, of the amounts of aqueous and hydrocarbon phases is chosen as high as possible, so as to obtain, after polymerization, an emulsion of high polymer content. Practically, this ratio may range, for example for about 0.5 to about 3:1, and usually approximates about 1:1, respectively. The one or more surfactants are selected in order to obtain HLB (Hydrophilic Lipophilic Balance) value ranging from about 8 to about 11. Outside this range, inverse emulsions are not usually obtained. In addition to the appropriate HLB value, the concentration of surfactant must also be optimized, i.e. sufficient to form an inverse emulsion. Too low a concentration of surfactant leads to inverse emulsions of the prior art and too high a concentrations results in undue costs. Typical surfactants useful, in addition to those specifically discussed above, may be anionic, cationic or nonionic and may be selected from polyoxyethylene (20) sorbitan trioleate, sorbitan trioleate, sodium di-2-ethylhexylsulfosuccinate, oleamidopropyldimethylamine; sodium isostearyl-2-lactate and the like. Polymerization of the emulsion may be carried out in any manner known to those skilled in the art. Initiation may be effected with a variety of thermal and redox free-radical initiators including azo compounds, such as azobisisobutyronitrile; peroxides, such as t-butyl peroxide; organic compounds, such as potassium persulfate and redox couples, such as ferrous ammonium sulfate/ammonium persulfate. Polymerization may also be effected by photochemical irradiation processes, irradiation, or by ionizing radiation with a 60 Co source. Preparation of an aqueous product from the emulsion may be effected by inversion by adding it to water which may contain a breaker surfactant. Optionally, the polymer may be recovered from the emulsion by stripping or by adding the emulsion to a solvent which precipitates the polymer, e.g. isopropanol, filtering off the resultant solids, drying and redispersing in water. The high molecular weight, ionic, synthetic polymers used in the present invention preferably have a molecular weight in excess of 100,000 and preferably between about 250,000 and 25,000,000. Their anionicity and/or cationicity may range from 1 mole percent to 100 mole percent. The ionic polymer may also comprise homopolymers or copolymers of any of the ionic monomers discussed above with regard to the ionic beads, with acrylamide copolymers being preferred. The degree of substitution of cationic starches (or other polysaccharides) and other non-synthetic based polymers may be from about 0.01 to about 1.0, preferably from about 0.02 to about 0.20. Amphoteric starches, preferably but not exclusively with a net cationic starch, may also be used. The degree of substitution of anionic starches (or other polysaccharides) and other non-synthetic-based polymers may be from 0.01 to about 0.7 or greater. The ionic starch may be made from starches derived from any of the common starch producing materials, e.g., potato starch, corn starch, waxy maize, etc. For example, a cationic potato starch made by treating potato starch with 3-chloro-2-hydroxypropyltrimethylammonium chloride. Mixtures of synthetic polymers and e.g. starches, may be used. Other polysaccharides useful herein include guar, cellulose derivatives such as carboxymethylcellulose and the like. It is also preferred that the high molecular weight, ionic polymer be of a charge opposite that of the microbead and that if a mixture of synthetic, ionic polymers or starch be used, at least one be of a charge opposite that of the microbead. The microbeads may be used as such or may be replaced in part, i.e. up to about 50%, by weight, with bentonite or a silica such as colloidal silica, modified colloidal silica etc. and still fall within the scope of the percent invention. The instant invention also relates to compositions for use in paper making comprising mixtures of the above-described ionic microbeads, high molecular weight, ionic polymers and polysaccharides. More particularly, compositions comprising a mixture of A) an ionic, organic, polymer microbead having an unswollen particle diameter of less than about 750 nanometers if cross-linked and less than 60 nanometers if non-cross-linked and water-insoluble and B) a high molecular weight ionic polymer, the ratio of A): B) ranging from about 1:400 to 400:1, respectively. Additionally, the compositions may contain the microbead A) and C) an ionic polysaccharide, the ratio of A):C) ranging from about 20:1 to about 1:1000, respectively. Still further, the compositions may contain the microbead A), the polymer B) and the polysaccharide C), the ratio of A) to B) plus C) ranging from about 400:1 to about 1:1000, respectively. Paper made by the process described above also constitutes part of the present invention. The following examples are set forth for purposes of illustration only and are not be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specificed. In the examples which follow, the ionic organic polymer microbead and/or the high molecular weight, ionic polymer and/or ionic starch are added sequentially directly to the stock or just before the stock reaches the headbox. Unless otherwise specified, a 70/30 hardwood/softwood bleached kraft pulp containing 25% CaCO 3 is used as furnish at a pH of 8.0. Retention is measured in a Britt Dynamic Drainage Jar. First Pass Retention (FPR) is calculated as follows: FPR = Headbox Consistency - Tray Water Consistency Head Box Consistency First Pass Retention is a measure of the percent of solids that are retained in the paper. Drainage is a measure of the time required for a certain volume of water to drain through the paper and is here measured as a 10x drainage. (K. Britt, TAPPI 63 (4) p67 (1980). Hand sheets are prepared on a Noble and Wood sheet machine. In all the examples, the ionic polymer and the microbead are added separately to the thin stock and subjected to shear. Except when noted, the charged microbead (or silica or bentonite) is added last. Unless noted, the first of the additives is added to the test furnish in a "Vaned Britt Jar" and subjected to 800 rpm stirring for 30 seconds. Any other additive is then added and also subjected to 800 rpm stirring for 30 seconds. The respective measurements are then carried out. Doses are given on kg/907 kg (pounds/ton) for furnish solids such as pulp, fillers etc. Polymers are given on a real basis, silica as SiO 2 and starch, clay and bentonite are given on an as is basis. I. Cationic polymers used in the examples are: Cationic Starch : Potato starch treated with 3-chloro-2-hydroxypropyltrimethylammonium chloride to give a 0.04 degree of substitution. 10 AETMAC/90 AMD : A linear cationic copolymer of 10 mole % of acryloxyethyltrimethylammonium chloride and 90 mole % of acrylamide of 5,000,000 to 10,000,000 mol. wt. with a charge density of 1.2 meq./g. 5 AETMAC/95 AMD: A linear copolymer of 5 mole % of acryloxyethltrimethylammonium chloride and 90 mole % of acrylamide of 5,000,000 to 10,000,000 mol. wt. 55 AETMAC/45 AMD: A linear copolymer of 55 mole % of acryloxyethyltrimethylammonium chloride and 45 mole % of acrylamide of 5,000,000 to 10,000,000 mol. wt. and a charge density of 3.97 meq./g. 40 AETMAC/60 AMD: A linear copolymer of 40 mole % of acryloxyethyltrimethylammonium chloride and 60 mole % of acrylamide of 5,000,000 to 10,000,000 mol. wt. 50 EPI/47 DMA 3 EDA: A copolymer of 50 mole % of epichlorohydrin, 47 mole % of dimethylamine and 3.0 mole % of ethylene diamine of 250,000 mol. wt. II. Anionic Polymers used in the examples are: 30 AA/70 AMD: A linear copolymer of 30 mole % ammonium acrylate and 70 mole % of acrylamide of 15,000,000 to 20,000,000 mol. wt. 7AA/93 AMD: A linear copolymer of 7 mole % ammonium acrylate and 93 mole % of acrylamide of 15,000,000 to 20,000,000 mol. wt. 10 APS/90 AMD: A linear copolymer of 10 mole % of sodium 2-acrylamido-2-methylpropanesulfonate and 90 mole % of acrylamide of 15,000,000 to 20,000,000 mol. wt. III. Anionic particles used in the examples are: SILICA: Colloidal silica with an average size of 5 nm, stabilized with alkali and commercially available. BENTONITE : Commercially available anionic swelling bentonite from clays such as sepiolite, attapulgite or montmorillonite as described in U.S. -A- 4,305,781. IV. Latices used in the examples are: Latex Particle Size in nm Anionic Charge Density nm 2 /Charge Group (Å 2 /Charge Group) Polystyrene 98 14 (1.4 x 10 3 ) Polystyrene 30 11 (1.1 x 10 3 ) Polystyrene 22 3.6 (0.36 x 10 3 ) V. Microbeads used in the examples are: 30 AA/70 AMD/50 ppm MBA: An inverse emulsion copolymer of 30 mole % of sodium acrylate and 70 mole % of acrylamide crosslinked with 50 ppm of methylenebisacrylamide with a particle diameter of 1,000-2,000*nm; SV-1.64 mPa.s. 40 AA/60 MBA: A microbead dispersion of a copolymer of 40 mole % of ammonium acrylate and 60 mole % of N,N'-methylenebisacrylamide (MBA) with a particle diameter of 220*nm. 30 AA/70 AMD/349 ppm MBA: A microemulsion copolymer of 30 mole % of sodium acrylate and 70 mole % of acrylamide crosslinked with 349 ppm of N,N'-methylenebisacrylanide (MBA) of 130*nm particle diameter, SV-1.17 to 1.19 mPa.s 30 AA/70 AMD/749 ppm MBA: A microemulsion copolymer of 30 mole % of sodium acrylate and 70 mole % of acrylamide crosslinked with 749 ppm of N,N'-methylenebisacrylamide (MBA), SV-1.06 mPa.s. 60 AA/40 AMD/1,381 ppm MBA: A microemulsion copolymer of 60 mole % of sodium acrylate and 40 mole % of acrylamide crosslinked with 1,381 ppm of N,N'-methylene-bis acrylamide (MBA) of 120* nm particle diameter; SV-1.10 mPa.s. 30 APS/70 AMD/995 ppm MBA: A microemulsion copolymer of 30 mole % of sodium 2-acrylamido-2-methylpropane sulfonate and 70 mole % of acrylamide cross-linked with 995 ppm of methylenebisacrylamide (MBA); SV-1.37 mPa.s. 30 AA/70 AMD/1000 ppm MBA/ 2% SURFACTANT (TOTAL EMULSION) : A microemulsion copolymer of 30 mole % of sodium acrylate and 70 mole % of acrylamide crosslinked with 1,000 ppm of N,N'-methylenebisacrylamide with 2% diethanolamide oleate and 464*nm particle diameter. 30 AA/70 AMD/1,000 ppm MBA/ 4% SURFACTANT (TOTAL EMULSION) : A microemulsion copolymer of 30 mole % of sodium acrylate and 70 mole % of acrylamide crosslinked with 1,000 ppm of N,N'-methylenebisacrylamide with 4% diethanolamide oleate and of 149*nm particle diameter, SV-1.02 mPa.s 30 AA/70 AMD/ 1,000 ppm MBA/ 8% SURFACTANT(TOTAL EMULSION) : A Microemulsion copolymer of 30 mole % of sodium acrylate and 70 mole % of acrylamide crosslinked with 1000 ppm of N,N'-methylenebisacrylamide with 8% diethanolamide oleate and of 106*nm particle diameter, SV-1.06 mPa.s. Procedure for the Preparation of Anionic Microemulsions 30 AA/70 AMD/349 ppm MBA - 130 nm An aqueous phase is prepared by sequentially mixing 147 parts of acrylic acid, 200 parts deionized water, 144 parts of 56.5% sodium hydroxide, 343.2 parts of acrylamide crystal, 0.3 part of 10% pentasodium diethylenetriaminepentaacetate, an additional 39.0 parts of deionized water, and 1.5 parts of 0.52% copper sulfate pentahydrate. To 110 parts of the resultant aqueous phase solution, 6.5 parts of deionized water, 0.25 part of 1% t-butyl hydroperoxide and 3.50 parts of 0.61% methylene bisacrylamide are added. 120 Parts of the aqueous phase are then mixed with an oil phase containing 77.8 parts of low odor paraffin oil, 3.6 parts of sorbitan sesquioleate and 21.4 parts of polyoxyethylene sorbitol hexaoleate. This resultant clear, microemulsion is deaerated with nitrogen for 20 minutes. Polymerization is initiated with gaseous SO 2 , allowed to exotherm to 40°C and controlled at 40°C (+ 5°C) with ice water. The ice water is removed when cooling is no longer required. The nitrogen is continued for one hour. The total polymerization time is 2.5 hours. For purposes of use in the instant process, the polymer may be recovered from the emulsion by stripping or by adding the emulsion to a solvent which precipitates the polymer, e.g. isopropanol, filtering off the resultant solids, and redispersing in water for use in the papermaking process. The precipitated polymer microbeads may be dried before redispersion in water. Alternatively, the microemulsion per se may also be directly dispersed in water. Depending on the surfactant and levels used in the microemulsion, dispersion in water may require using a high hydrophilic lipopilic balance (HLB) inverting surfactant such as ethoxylated alcohols; polyoxyethlated sorbitol hexaoleate; diethanolamine oleate; ethoxylated laurel sulfate et. as in known in the art. The concentration of the microbeads in the above-described redispersion procedures is similar to that used with other thin stock additives, the initial dispersion being at least 0.1%, by weight. The dispersion may be rediluted 5-10 fold just before addition to the papermaking process. Preparation of Cationic Organic Microbead 40 AETMAC/60 AMD/100 ppm MBA - 100 nm By microemulsion Polymerization An aqueous phase containing 21.3 parts, by weight of acrylamide, 51.7 parts of a 75% acryloxyethyltrimethyl ammonium chloride solution, 0.07 part of 10% diethylenetriamine pentaacetate (penta sodium salt), 0.7 part of 1% t-butyl hydroperoxide and 0.06 part of methylenebisacrylamide dissolved in 65.7 parts of deionized water is prepared. The pH is adjusted to 3.5 (±0.1). An oil phase composed of 8.4 parts of sorbitan sesquioleate, 51.6 parts of polyoxyethylene sorbitol hexaoleate dissolved in 170 parts of a low odor paraffin oil is prepared. The aqueous and oil phase are mixed together in an air tight polymerization reactor fitted with a nitrogen sparge tube, thermometer and activator addition tube. The resultant clear microemulsion is sparged with nitrogen for 30 minutes and the temperature is adjusted to 27.5°C. Gaseous sulfur dioxide activator is then added by bubbling nitrogen through a solution of sodium metabisulfite. The polymerization is allowed to exotherm to its maximum temperature (about 52°C) and then cooled to 25°C. The particle diameter of the resultant polymer microbead is found to be 100 nm. The unswollen number average particle diameter in nanometers (nm) is determined by quasi-elastic light scattering spectroscopy (QELS). The SV is 1.72 mPa.s. Preparation of Cationic Organic Inverse Emulsion 40 AETMAC/60 AMD/100 ppm MBA 1,000 nm by Inverse Emulsion Polymerization An aqueous phase is made by dissolving 87.0 parts of commercial, crystal acrylamide (AMD), 210.7 parts of a 75% acryloxyethyltrimethylammonium chloride (AETMAC) solution, 4.1 parts of ammonium sulfate, 4.9 parts of a 5% ethylene diaminetetraacetic acid (disodium salt) solution, 0.245 part (1000 wppm) of methylenebisacrylamide (MBA) and 2.56 parts of t-butyl hydroperoxide into 189 parts of deionized water. The pH is adjusted to 3.5 (±0.1) with sulfuric acid. The oil phase is made by dissolving 12.0 gms of sorbitan monooleate into 173 parts of a low odor paraffin oil. The aqueous phase and oil phase are mixed together and homogenized until the particle size is in the 1.0 µm range. The emulsion is then transferred to a one liter, three-necked, creased flask equipped with an agitator, nitrogen sparge tube, sodium metabisulfite activator feed line and a thermometer. The emulsion is agitated, sparged with nitrogen and the temperature adjusted to 25°C. After the emulsion is sparged 30 minutes, 0.8% sodium metabisulfite (MBS) activator solution is added at a 0.028 ml/minute rate. The polymerization is allowed to exotherm and the temperature is controlled with ice water. When cooling is no longer needed, the 0.8% MBS activator solution/addition rate is increased and a heating mantle is used to maintain the temperature. The total polymerization time takes approximately 4 to 5 hours using 11 mls of MBS activator. The finished emulsion product is then cooled to 25°C. The particle diameter is found to be 1,000 nm. The unswollen number average particle diameter in nanometers is determined by the quasi-elastic light scattering spectroscopy (QELS). The SV is 1.24 mPa.s. EXAMPLE 1 Using the paper-making procedure described above, the drainage times are measured on 1) alkaline stock containing 5% CaCO 3 , alone, 2) the same stock with added linear, high molecular weight cationic copolymer of 10 mole % acryloxyethyltrimethylammonium chloride and 90 mole % of acrylamide (10 AETMAC/90 AMD) and 3) the same stock with added cationic copolymer and anionic microbead made from 30 mole % acrylic acid 70 mole % of acrylamide (30 AA/70 AMD) and cross-linked with 349 ppm of methylenebisacrylamide (MBA) of 130 nm particle diameter and added as a redispersed 0.02% aqueous solution. The results are shown in Table I, below. Cationic Polymer Anionic Microbead Drainage in Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 88.4 0.91 (2) 0 (0) 62.3 0.91 (2) 0.22 (0.5) 37.5 The addition of cationic polymer reduces drainage time from 88.4 to 62.3 seconds. Surprisingly microbeads reduce the drainage times by another 24.8 seconds to 37.5 seconds, a 39.8% reduction which is a significant improvement in drainage times. EXAMPLE 2 The alkaline furnish used in this example contains 2.27 kg/907 kg (5.0 lbs/ton) of cationic starch. To this furnish is added to following additives as described in Example 1. Drainage times are then measured and reported in Table II, below. Cationic Polymer Anionic Microbead Drainage in Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/ton) 0 (0) 0 (0) 121.9 0.45 (1) - 10 AETMAC/90 AMD 0 (0) 89.6 0.45 (1) - 10 AETMAC/90 AMD 0.22 (0.5) - 30 AA/70 AMD/349 ppm-130 nm 57.8 In the presence of a mixture of high molecular weight cationic polymer and, cationic starch, anionic polymer microbeads greatly improves drainage. EXAMPLE 3 Following the procedure of Example 1, various other comparative runs are made using a second alkaline stock containing 10 lbs/ton of cationic starch, and bentonite, as disclosed in U.S. -A- 4,753,710, in order to show the benefits of the use of organic microbeads in accordance with the invention hereof. The results are shown in Table III, below. Cationic Polymer Anionic Micro-Particle Drainage in Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) (0) (0) 132.3 0.45 (1.0)- 10 AETMAC/90 AMD 2.27 (5.0)- Bentonite 53.1 0.45 (1.0)- 10 AETMAC/90 AMD 0.22 (0.5)- 30 AA/70 AMD/349 ppm MBA - 130 nm 55.1 0.45 (1.0)- 10 AETMAC/90 AMD 0.22 (0.5)- 100AA-1985 ppm MBA-80 nm 65.1 0.45 (1.0)- 55 AETMAC/45 AMD 2.27 (5.0)- Bentonite 76.4 0.45 (1.0)- 55 AETMAC/45 AMD 0.22 (0.5)- 30 AA/70 AMD/349 ppm MBA - 130 nm 55.4 0.45 (1.0)- 55 AETMAC/45 AMD 0.22 (0.5)- 60 AA/40 AMD/1,381 ppm MBA - 120 nm 45.7 0.45 (1.0)- 55 AETMAC/45 AMD 0.22 (0.5)- 100AA-1985 ppm MBA 48.6 When the 10% cationic polymer AETMAC/AMD (10/90) is used in conjunction with 2.27 kg (5.0 lbs) of bentonite, similar drainage results to those obtained using only 0.22 kg (0.5 lb.) of 30% anionic microbead AA/AMD (30/70) in place of the bentonite, are obtained. With a 55% cationicity polymer, bentonite gives a slower drainage rate of 76.4 seconds and the 30% anionic microbead about the same drainage rate of 55.4 seconds. With the higher cationicity polymer (55%) and 0.22 kg (0.5 lbs/ton) of a high anionicity microbead, AA/AMD (60/40) a far superior drainage time of 45.7 seconds is obtained, using far less additive. EXAMPLE 4 An alkaline paper stock containing 5kg/907 kg (10 pounds/ton) of cationic starch is treated as described in Example 1. The results are shown in Table IV, below. Cationic Polymer Anionic Micro-Particle Drainage in Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 115.8 0.22 (0.5)- 10 AETMAC/90 AMD 0 (0) 83.5 0.22 0.5)- 10 AETMAC/90 AMD 2.27 (5.0)- Bentonite 51.1 0.22 (0.5)- 10 AETMAC/90 AMD 0.22 (0.5)- 30AA/70 AMD/349 ppm MBA - 130 nm 57.3 0.22 (0.5)- 55 AETMAC/45 AMD 0.22 (0.5)- 60AA/40 AMD/1,381 ppm - 120 nm 46.1 0.45 (1.0)- 10 AETMAC/90 AMD 2.27 (5.0)- Bentonite 42 0.45 (1.0)- 55 AETMAC/45 AMD 0.22 (0.5)- 60 AA/40 AMD/1,381 ppm MBA - 120 nm 38.9 The combination of 0.22 kg/907 kg (0.5 lb/ton) of cationic polymer and 2.27 kg/907 kg (5.0 lbs/ton) of bentonite gives a good drainage of 51.5 seconds, somewhat better than the 0.22 kg (0.5 lb) of 30% anionicity microbeads, i.e. 57.3 seconds. However, bentonite is inferior to the results achieved using 0.22 kg/907 kg (0.5 lb/ton) of a higher (60%) anionicity polymer, i.e. of 46.1 seconds. Increasing the amount of cationic polymer to 0.45 kg/907 kg (1.0 lb/ton) results in improved bentonite and 60% anionic polymer microbead times of 42 and 38.9 seconds, however, the microbead results are again superior. EXAMPLE 5 The procedure of Example 1 is again followed except that first pass retention values are measured. The organic anionic microbead is compared at a 0.22 kg/907 kg (0.5 lbs/ton) rate to 0.91 kg/907 kg (2.0 lbs/ton) of silica and 2.27 kg/907 kg (5.0 lbs/ton) of bentonite in an alkaline paper stock as known in the art. The organic, 30% anionic polymer microbeads give the best retention values at a lower concentration, as shown in Table V, below. Cationic Polymer Anionic Microbead Fines First Pass Retention in % kg/907 kg (lbs/Ton) kg/907 kg (lbs/ton) 0.91 (2.0) - 10 AETMAC/90 AMD (0) 50.3 0.91 (2.0) - 10 AETMAC/90 AMD 0.91 (2.0)- Silica- 5nm 55.3 0.91 (2.0) - 10 AETMAC/90 AMD 2.27 (5.0)- Bentonite 55.8 0.91 (2.0) - 10 AETMAC/90 AMD 0.22 (0.5)- 30 AA/70 AMD/749 ppm MBA 59.2 EXAMPLE 6 The procedure of Example 1 is again followed except that alum is added to the stock immediately before the cationic polymer. The test furnish is alkaline stock containing 2.27 kg/907 kg (5.0 lbs/ton) of cationic starch and 25% CaCO 3 . The results are set forth below in Table VI. Cationic Polymer Anionic Microbead Drainage in Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/ton) 2.27 kg/907 kg(5lbs/ton)Alum 0.22 (0.5) - 10 AETMAC/90 AMD 2.27 (5) - Bentonite 46.1 0.22 (0.5) - 10 AETMAC/90 AMD 0.22 (0.5) - 30 AMD/349 ppm MBA - 130 nm 39.9 4.53 kg/907 kg(10 lbs/ton)Alum 0.45 (1) - 10 AETMAC/90 AMD 2.27 (5) - Bentonite 33.5 0.45 (1) - 10 AETMAC/90 AMD 0.22 (0.5) - 30 AA/70 AMD/349 ppm - 130 nm 29.6 The alum-treated furnish which is contracted with the polymer microbead has a faster drainage rate than that treated with 10 times as much bentonite. In a comparative test using 0.22 kg (0.5 lb) of 10 AETMAC/90 AMD and 2.27 kg (5.0 lbs) bentonite without alum, an equivalent drainage time of 46.1 seconds, is achieved. EXAMPLE 7 This example demonstrates the greater efficiency of the anionic organic polymer microbeads of the present invention used with alum as compared to bentonite alone. This efficiency is not only attained using a significantly lower anionic microbead dose but, also enable the use of a lower amount of cationic polymer. The furnish is alkaline and contains 2.27 kg (5.0 lbs/ton) of cationic starch. The procedure of Example 1 is again used. The results are shown in Table VII, below. Cationic Polymer Alum Anionic Microbead Drainage in Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/ton) (0) 0 (0) 0 (0) 103.4 0.22 (0.5)- 10 AETMAC/90 AMD 0 (0) 0 (0) 87.5 0.22 (0.5)- 10 AETMAC/90 AMD 2.27 (5) 0 (0) 76.4 0.22 (0.5)- 10 AETMAC/90 AMD 2.27 (5) 0.11 (0.25)-30 AA/70 AMD/349 ppm MBA - 130 nm 51.1 0.22 (0.5)- 10 AETMAC/90 AMD 2.27 (5) 0.22 (0.50)-30 AA/70 AMD/349 ppm MBA-130 nm 40.6 0.22 (0.5)- 10 AETMAC/90 AMD 0 (0) 2.27 (5) - Bentonite 51.6 0.45 (1.0)- 10 AETMAC/90 AMD 0 (0) 2.27 (5) - Bentonite 40.2 Thus, at a 0.22 kg (0.5 lb) cationic polymer addition level, the anionic organic microbeads used with alum are approximately 20 fold more efficient than bentonite used alone (0.12 kg vs. 0.22 kg) (0.25 lb. vs. 5.0 lbs). The cationic polymer level can be reduced in half (0.22 kg vs. 0.5 kg) (0.50 lb. vs. 1.0 lb.) compared to bentonite when the microbead level is raised to 0.22 kg (0.50 lb), which is 10 fold lower than the bentonite dose. EXAMPLE 8 The procedure of Example 7 is again followed except that polyaluminum chloride is used in place of alum. As can be seen, in Table VIII, equivalent results are achieved. Cationic Polymer Aluminium Salt Anionic Microbead Drainage in Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/ton) 0.22 (0.5)- 10 AETMAC/90 AMD 0 (0) Bentonite 57.5 0.22 (0.5) - 10 AETMAC/90 AMD 2.27 (5)-Alum 0.22 (0.5)- 30 AA/70 AMD/349 ppm - 130 nm 41.5 0.22 (0.5)- 10 AETMAC/90 AMD 3.85 (8.5)-Poly-aluminum Chloride (2.27 (5.0 lbs)alum (eqivalent)) 0.22 (0.5)- 30 AA/70 AMD/349 ppm - 130 nm 42.0 EXAMPLE 9 To a batch of alkaline paper stock is added cationic starch. The drainage time is measured after addition of the following additives set forth in Table IX, below. The procedure of Example 1 is again used. Cationic Polymer Anionic Microbead Drainage (Sec.) 2.27/907 kg (5.0 lbs/Ton) Drainage (Sec.) 4.53kg/907 kg (10 lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) Starch Starch 0.22 (0.5)- 10 AETMAC/90 AMD 2.27 (5)- Bentonite 46.9 50.9 0.22 (0.5)- 10 AETMAC/90 AMD plus 5 lbs Alum 0.22 (0.5)- 30 AA/70 AMD/349 ppm MBA - 130 nm 34.0 32.7 C = Comparative Test The alum/polymer microbead combination gives better drainage rates than the polymer/bentonite combination without alum. EXAMPLE 10 First pass retention is measured on an alkaline furnish containing 2.27 kg/907 kg (5.0 lbs/ton) of starch to which the additives of Table X, below,are added. Anionic Microbead Fines First Pass Retention 10 AETMAC/90 AMD kg/907kg(lbs/Ton) kg/907 kg (lbs/Ton) 0.22 (0.5) 0.45 (1.0) 0.91 (2.0) 2.27 (5.0) - Bentonite 39.9% 41.6% 46.8% 2.27 ( 5.0)- 30 AA/70 AMD/349 ppm MBA - 130 nm 39.9% 44.4% 48.5% The microbead and bentonite give similar retentions with 0.22 kg/907 kg (0.5 lb/ton) of cationic polymer but with higher concentrations of polymer better retention is obtained with the microbeads. EXAMPLE 11 Another alkaline paper furnish containing 2.27 kg/907 kg bs/ton) of cationic starch and 1.13 kg/907 kg (2.5 lbs/ton) of alum to which the additives of Table XI are added as in Example 10, is treated. Anionic Microbead Fines First Pass Retention 10 AETMAC/90 AMD kg/907kg(lbs/Ton) kg/907 kg (lbs/Ton) 0.22 (0.5) 0.45 (1.0) 2.27 (5) - Bentonite 34.6% 42.3% 3.17 (7) - Bentonite - 43.1% 0.11 (0.25)- 30 AA/70 AMD/349 ppm MBA - 130 nm 35.7% 43.4% 0.22 (0.5) - 30 AA/70 AMD/349 ppm MBA - 130 nm 38.7% 44.6% A significant reduction in the dosages of polymeric microbead results in equivalent or superior retention properties. EXAMPLE 12 Lower molecular weight, cationic, non-acrylamide based polymers are used in papermaking and in this example the effect of anionic microbeads on the performance of a polyamine of said class is set forth. To an alkaline furnish containing 2.27 kg/907 kg (5 lbs/ton) of cationic, starch is added 0.45 kg/907 kg (1.0 lb/ton) of a cationic polymeric polymer of 50 mole % epichlorohydrin, 47 mole % dimethylamine and 3.0 mole % ethylenediamine of 250,000 mol. wt. The polyamine is used alone and in combination with 0.22 kg/907 kg (0.5 lbs/ton) of microbead copolymer of 60% acrylic acid and 40% acrylamide cross linked with 1,381 ppm of methylenebisacrylamide and having 120 nm diameter particle size. From the data of Table XII it is seen that addition of the highly effective organic microbead cuts drainage time in half from 128.1 to 64.2 seconds. Cationic Polymer Anionic Microbead Drainage In Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0 (0) 0 (0) 138.8 0.45 (1) 0 (0) 128.1 0.45 (1) 0.22 (0.5) 64.2 EXAMPLE 13 In order to evaluate the use of microbeads on mill stock, a test is run on stock from a commercial paper mill. The paper stock consists of 40% hardwood/30% soft wood/30% broke containing 12% calcium carbonate, 4% clay, and 1.27 kg/907 kg (2.5 lbs/ton) of alkyl succinic anhydride (ASA) synthetic size emulsified with 5 kg/907 kg (10 lbs/ton) cationic potato starch. An additional 2.72 kg/907 kg (6 lbs/ton) of cationic potato starch and 2.72 kg/907 kg (6 lbs/ton) of alum are also added to this stock. The additives listed in Table XIII, below, are added and drainage times are measured, as in Example 1. Cationic Polymer Anionic Microbead Drainage In Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0 (0) 0 (0) 153.7 0.22 (0.5)- 10 AETMAC/90 AMD 0 (0) 112.8 0.22 (0.5)- 10 AETMAC/90 AMD 2.27 (5.0)- Bentonite 80.3 0.22 (0.5)- 10 AETMAC/90 AMD 0.11 (0.25)-30 AA/ 70 AMD-349 ppm MBA - 130 nm 69.9 0.22 (0.5)- 10 AETMAC/90 AMD 0.22 (0.5)-30 AA/ 70 AMD-349ppm MBA - 130 nm 57.5 0.45 (1.0)- 10 AETMAC/90 AMD 2.27 (5.0) - Bentonite 71.9 0.45 (1.0)- 10 AETMAC/90 AMD 0.22 (0.5)-30 AA/ 70 AMD-349ppm MBA - 130 nm 49.1 The paper stock from the above run has a 153.7 second drainage time. Significant reduction of drainage time to 80.3 seconds is achieved with 0.22 kg/907 kg (0.5 lb/ton) of high molecular weight, cationic polymer and 2.27 kg/907 kg (5 lbs/ton) of bentonite. Replacement of the bentonite with a mere 0.11 kg/907 kg (0.25 lb/ton) of organic anionic microbeads reduces drainage time another 10.7 seconds to 69.9 seconds. Thus, the microbeads at 1/20 the concentration give a superior drainage time to bentonite. The use of 0.22 kg/907 kg (0.5 lb/ton) of the microbeads reduces the drainage time to 57.5 seconds. This is 22.8 seconds faster than ten times the weight of bentonite. When testing is carried out using 0.45 kg/907 kg (1.0 lb/ton) of cationic polymer and 2.27 kg/907 kg (5.0 lbs/ton) of bentonite, drainage time is 71.9 seconds. However, when the test is performed with 0.22 kg (0.5 lb) of microbeads, the drainage time is 49.1 seconds which is 22.8 seconds faster than bentonite with one tenth the amount of microbead. EXAMPLE 14 The effect of using a cationic polymer of a lower charge density is investigated on the paper stock that was used in proceeding Example 13 and shown in Table XIV. The cationic polymer used, 5 AETMAC/95 AMD, has one half the charge density as that of 10 AETMAC/90 AMD that was used in Example 13. All else remains the same. Cationic Polymer Additional Alum Microbead Drainage in Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0.22 (0.5)- 5 AETMAC/95 AMD 0 (0) 0 (0) 94.7 0.22 (0.5)- 5 AETMAC/95 AMD 0 (0) 2.27 (5)-Bentonite 51.4 0.22 (0.5)- 5 AETMAC/95 AMD 1.13 (2.5) 2.27 (5)-Bentonite 56.7 0.22 (0.5)- 5 AETMAC/95 AMD 0 (0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 48.7 0.22 (0.5)- 5 AETMAC/95 AMD 1.13 (2.5) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 39.5 The superiority of 1/10th the amount of polymeric microbead to bentonite is evident with a lower charge cationic polymer also. Furthermore, the drainage time of cationic polymer and bentonite did not improve but decreased by 5.3 sec. on further addition of 1.13 kg/907 kg (2.5 lbs/ton) of alum. EXAMPLE 15 The effect of changing the amount of starch on drainage time is measured by not incorporating the 2.72 kg/907 kg (6.0 lbs/ton) of additional starch added to the furnish in Example 13 using the same stock . The results are shown in Table XV. Cationic Polymer Additional Alum Microbead Drainage in Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0.22 (0.5)- 5 AETMAC/95 AMD 0 (0) 2.27 (5)-Bentonite 45.9 0.22 (0.5)- 5 AETMAC/95 AMD 0 (0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 39.5 0.22 (0.5)- 5 AETMAC/95 AMD 1.13 (2.5) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 29.5 EXAMPLE 16 To evaluate the effect of the charge density of the cationic polymer on retention, to the furnish of Example 13, are added the additives shown in Table XVI. First pass retention values are measured, as in Example 5. Polymer microbeads are shown to be effective when used with high molecular weight, cationic polymers of lower charge density. EXAMPLE 17 A stock is taken from a second commercial mill. It is a goal of this example to demonstrate that microbeads/alum give equivalent drainage times to those of current commercial systems. The mill stock consists of 45% deinked secondary fiber/25% softwood/30% broke containing 15% calcium carbonate and 1.36 kg/907 kg (3.0 lbs/ton) of alkyl ketene dimer synthetic size emulsified with 4.53 kg/907 kg (10 lbs/ton) of cationic starch. A second portion of 4.53 kg (10 lbs) of cationic starch is added to the thick stock and the ingredients listed in Table XVII, below are added to the furnish, as described in Example 1. Cationic Polymer Alum Anionic Microbead Drainage in Seconds kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0.27 (0.6) 10 AETMAC/90 AMD 0 (0) 2.27 (5)-Bentonite 158.2 0.27 (0.6) 10 AETMAC/95 AMD 2.27 (5.0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 141.6 The microbeads/alum gives a faster drainage rate than the commercial bentonite system used in the mills routine production of paper. Other experimental runs result in lesser conclusive effectiveness with this pulp. EXAMPLE 18 Microbead retention efficiency is evaluated on papers made using a pilot Fourdrinier papermaking machine. The paper stock consists of pulp made from 70% hardwood and 30% softwood containing 25% calcium carbonate and 2.27 kg/907 kg (5 lbs/ton) of cationic starch. The additives in the Table XVIII, below, are placed into the furnish in successive runs and first pass retention percentages are measured. A 24 kg (46 lb) base weight paper is made. The cationic, high molecular weight polymer is added just before the fan pump, the anionic microbead is added just before the pressure screen and alum, when added, is added just before the cationic polymer. Results are set forth in Table XVIII, below. Cationic Polymer Alum Anionic Microbead Ash-First Retention % kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0 (0) 0 (0) 0 (0) 34.4 % 0.27 (0.6) 10 AETMAC/90 AMD 0 (0) 3.17 (7.0)-Bentonite 61.3 % 0.27 (0.6) 10 AETMAC/90 AMD 1.13 (2.5) 0.11 (0.25)-30 AA/70 AMD/349 ppm MBA-150 nm SV-1.32 62.7 % 0.27 (0.6) 10 AETMAC/90 AMD 1.13 (2.5) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-150 nm SV-1.32 67.0 % In this example, the combination of 0.22 kg/907 kg (0.5 lb/ton) of microbeads and 1.13 kg/907 kg (2.5 lbs/ton) of alum results in a 5.7% superior retention over 3.17 kg/907 kg (7.0 lbs/ton) of bentonite alone. The 3.17 kg/907 kg (7.0 lbs/ton) of bentonite is about equal to the combination of 0.11 kg (0.25 lbs) of beads and 1.13 kg/907 kg (2.5 lbs/ton) of alum in retention properties, a significant dosage reduction. EXAMPLE 19 The same pilot paper machine and paper stock that was used in Example 18 is again used except that a 24.94 kg (55 lb) "basis weight" paper is made. Additives in Table XIX, below, are mixed into the furnish as in the preceding example on successive runs and retention values are measured. Cationic Polymer Alum Anionic Microbead Ash-First Pass Retention % kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0 (0) 0 (0) 0 (0) 39.3 % 0.27 (0.6) 10 AETMAC/90 AMD 0 (0) 0 (0) 39.4 % 0.27 (0.6) 10 AETMAC/90 AMD 0 (0) 3.17 (7.0)-Bentonite 74.6 % 0.27 (0.6) 10 AETMAC/90 AMD 1.13 (2.5) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-150 nm SV-1.32 74.5 % 0.27 (0.6) 10 AETMAC/90 AMD 2.27 (5.0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-150 nm SV-1.32 74.7 % In comparing the heavier (24.94 kg (55 lb)) basis weight paper of Examble 19 to that of Example 18 (20.86 kg (46 lb)), under all conditions, the heavier paper has better retention. With the heavier paper there is no significant difference in retention between the paper prepared with bentonite alone and that prepared with microbeads and either 1.13 kg (2.5 lbs) or 2.27 kg (5 lbs) of alum, except the significant dosage reduction ie 3.17 kg (7 lbs) vs. 0.22 kg (0.5 lb) EXAMPLE 20 The effect of microbead on paper formation is evaluated by treatment of an alkaline furnish containing 2.27 kg/907 kg (5.0 lbs/ton) of starch with the additives listed in Table XX, below, as described in Example 18. Cationic Polymer Alum Anionic Microbead Paprican Microscanner SP/RMS Ratio kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) kg/907kg (lbs/Ton) 0.45 (1) 10 AETMAC/90 AMD 0 (0) 2.27 (5)-Bentonite 66 0.45 (1) 10 AETMAC/90 AMD 0 (0) 0.45 (1)-30 AA/70 AMD/349 ppm MBA-130 nm 69 EXAMPLE 21 Using the paper stock of Example 20, except that the cationic starch concentration is increased to 4.53 kg/907 kg (10 lbs/ton), formation is measured on paper made with the additives set forth in Table XXI. Microbeads give superior hand sheet paper formation and better drainage times compared to bentonite, and at a lower dosage. EXAMPLE 22 To an alkaline furnish containing 2.27 kg (5 lbs) of cationic starch, the ingredients set forth in Table XXII are added to the furnish of Example 21 and formation is observed visually on the paper hand sheets, produced thereby. Hand sheets from the first three samples have equivalent formation (A) by visual observation. The last two samples (B) themselves have equivalent formation by visual observation but their formation is not as good as the first three sheets. The experiment shows the superior drainage times are achieved with a microbead alum combination with equivalent visual paper formation as compared to bentonite, above, at higher dosage. EXAMPLE 23 In order to evaluate a different type of anionic microparticle, three different particle sizes of hydrophobic polystyrene microbeads, stabilized by sulfate charges, are added to an alkaline paper stock containing 25% CaCO 3 and 2.27 kg/907 kg (5 lbs/ton) of cationic starch in the furnish. Table XXIII sets forth the additives used and drainage times measured. Cationic Polymer Anionic Polystyrene Microbeads Drainage Sec. kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 103.9 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 0 (0) 91.6 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 2.27 (5.0)-Polystyrene beads-98 nm 79.8 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 2.27 (5.0)-Polystyrene beads-30 nm 49.9 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 2.27 (5.0)-Polystyrene beads-22 nm 42.2 Sec. It is noted that all three anionic poly-stryene microbeads improved drainage time over the cationic polymer alone with the smallest bead being the most effective. The results indicate that noncross-linked, polymeric, water-insoluble microbeads are effective in increasing drainage rates. EXAMPLE 24 A 30 nm polystyrene bead is compared to bentonite in performance using the alkaline paper stock containing 2.27 kg/907 kg (5.0 lbs/ton) of cationic starch, above described in Example 22. Results are set forth in Table XXIV. Cationic Polymer Anionic Microbead Drainage Sec. kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0.45 (1.0) 10 AETMAC/90 AMD 0 (0) 70.9 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 2.27 (5.0)-Bentonite 28.5 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 2.27 (5.0)-Polystyrene Beads-30 nm 30.5 Sec. The results indicate that the 30nm polystyrene is substantially equivalent to bentonite. EXAMPLE 25 Microbead size of anionic polymer is studied by measuring drainage rates on the alkaline paper stock of Example 23 to which the additives of Table XXV are added. Results are specified therein. Cationic Polymer Anionic Microbead Drainage Sec. kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0.45 (1.0) 10 AETMAC/90 AMD 0 (0) 106.8 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 72.2 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 0.91 (2.0)-40 AA/60 MBA-220 nm 71.7 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 0.22 (0.5)-30 AA/70 AMD/50 ppm MBA-1,000-2,000 nm 98.9 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 0.91 (2.0)-30 AA/70 AMD/50 ppm MBA-1,000-2,000 nm 103.6 Sec. Both the 130 nm and 220 nm in diameter microbeads reduce drainage times over that of stock without microbeads by 33%. However, when the diameter of the anionic microbead is increased to 1,000 to 2,000 nm, drainage is not significantly effected. EXAMPLE 26 Using the same paper stock as in Example 22 the ingredients shown in Table XXVI are added in successive order, as in the previous examples. The results are specified. Cationic Polymer Anionic Microbead Drainage Sec. kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 135.6 Sec. 0.45 (1.0) 55 AETMAC/45 AMD 0 (0) 99.6 Sec. 0.45 (1.0) 55 AETMAC/45 AMD 0.22 (0.5)-30 AA/70 AMD/1000 ppm MBA-2% surfactant-464 nm 86.7 Sec. 0.45 (1.0) 55 AETMAC/45 AMD 0.22 (0.5)-30 AA/70 AMD/1000 ppm MBA-4% surfactant-149 nm 59.3 Sec. 0.45 (1.0) 55 AETMAC/45 AMD 0.22 (0.5)-30 AA/70 AMD/1000 ppm MBA-8% surfactant-106 nm 54.5 Sec. Increased drainage rate is achieved as the microbead becomes smaller. Compared to the drainage time of 99.6 seconds without microbeads, the 464nm microbead results in a 12.9% reduction and the 149nm microbead a 40% reduction, showing the effect of small diameter organic microparticles. EXAMPLE 27 To the same stock that was used in Example 23, the ingredients set forth in Table XXVII are added, as in said example. Cationic Polymer Anionic Microbead Drainage Sec. kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0.45 (1.0) 10 AETMAC/90 AMD 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 66.3 Sec. 0.45 (1.0) 10 AETMAC/90 AMD 0.22 (0.5)-30 APS/70 AMD/995 ppm MBA SV-1.37 mPa.s 67.0 Sec. The microbeads of the 30 AA/70 AMD/349 ppm MBA copolymer and those of the 30 APS/70 AMD/995 ppm MBA copolymer when used with cationic polymers, produces paper with almost identical drainage times, even though one has a carboxylate and the other has a sulfonate functional group. That the anionic beads have different chemical compositions and a differing degree of cross-linking yet yield similar properties is attributed to this similar charge densities and similar particle size. The acrylic acid microbead has a diameter of 130 nm and the 2-acrylamido-2-methyl-propane sulfonic acid microbead is of a similar size due to the similar way it was made. EXAMPLE 28 The effect of different shear conditions on the relative performance of the anionic microbead compared to bentonite is shown in Tables XXVII A & B. Drainage testing is carried out as described in Example 1, on an alkaline furnish containing 2.27 kg (5.0 lbs) of cationic starch subjected to four different shear conditions. Condition Stirring R.P.M. and Time* Cationic Polymer Microbead A 800 rpm-30 sec. 800 rpm-30 sec. B 1,500 rpm-30 sec. 800 rpm-30 sec. C 1,500 rpm-60 sec. 800 rpm-30 sec. D 1,500 rpm-60 sec. 1,500 rpm-5 sec. High molecular weight cationic polymer is added to the furnish in a vaned Britt jar under agitation and agitation is continuous for the period specified before the microbead is added as in Example 1, agitation is continued, and the drainage measurement taken. Cationic Polymer Anionic Microbead Drainage in Seconds Shear Conditions A B C D 0.27 kg (0.6 lbs) 10 AETMAC/90 AMD 2.27 kg (5.0 lbs) Bentonite 52.6 56.1 57.8 49.6 0.27 kg (0.6 lbs ) 10 AETMAC/90 AMD 0.22 kg (0.5 lbs)30AA/70 AMD-349 ppm MBA-130 nm 45.9 48.3 52.3 44.5 The relative performance of each additive system remains the same under different test shear conditions. EXAMPLE 29 The utility of polymeric anionic microbeads in acid paper stock is established as follows. To an acid paper stock made from 2/3 chemical pulp 1/3 ground wood fiber, and containing 15% clay and 4.53 kg/907 kg (10 lbs/ton) of alum at a pH of 4.5 are added and the listed ingredients of Table XXIX below. Anionic Microbead Drainage using Cationic Polymer 10 AETMAC/90 AMD Drainage using Cationic Polymer 10 AETMAC/90 AMD kg/907 kg (lbs/Ton) 0.22 kg/907 kg (0.5 lb/Ton) 0.45 kg/907 kg (1 lb/Ton) 0 (0) 64.2 Sec. 52.2 Sec. 2.27 (5.0)-Bentonite 57.0 Sec. 47.0 Sec. 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 53.3 Sec. 42.1 Sec. 0.45 (1.0)-30 AA/70 AMD/349 ppm MBA-130 nm -- 38.7 Sec. Thus, in acid paper processes, 0.22 kg (0.5 lb) of polymeric anionic microbeads is superior to 2.27kg (5.0 lbs) of bentonite in increasing drainage. At a level of 0.45 kg/907 kg (1.0 lb/ton) of cationic polymer, 2.27 kg/907 kg (5.0 lbs/ton) of bentonite lowers drainage time 10% while 0.22 kg/907 kg (0.5 lb/ton) of microbeads lowers it 19.3% and 0.45 kg/907 kg (1.0 lb/ton) of microbeads lowers it 25.9%. EXAMPLE 30 This example demonstrates the effect of alum on drainage in the acid paper process when acid stock from Example 29 is used without initial alum addition. A set of drainage times is measured for this stock without alum present and a second series is measured with 2.27 kg/907 kg (5.0 lbs/ton) of added alum and with the ingredients set forth in Table XXX. The enhancement of drainage time with the added alum is a significant advantage of the present invention. Cationic Polymer Anionic Microbead Drainage in Seconds Alum in Stock kg/907 kg (lbs/Ton) kg/907 kg (lb/Ton) -0- 2.27 kg/907 kg (5 lbs/Ton) 0.45 (1.0)-10 AETMAC/90 AMD 2.27 (5.0)-Bentonite 43.0 43.5 0.45 (1.0)-55 AETMAC/45 AMD 0.45 (1.0)-30 AA/70 AMD/ 349 ppm MBA-130 nm 42.1 29.1 C = Comparative Test EXAMPLE 31 In recent years cationic potato starch and silica have been found to give improved drainage times when used in alkaline papermaking processes. The effectiveness of polymeric microbeads compared to the silica system is shown in Table XXXI using the ingredients set forth therein on to the alkaline paper stock of, and in accordance with, Example 1. Cationic Potato Starch Alum Anionic Microbead Drainage Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 0 (0) 119.1 6.80 (15)-Starch 0 (0) 0 (0) 112.7 6.80 (15)-Starch 2.27 (5.0) 0 (0) 84.3 6.80 (15)-Starch 2.27 (5.0) 1.36 (3.0)-Silica-5 nm 38.5 6.80 (15)-Starch 2.27 (5.0) 0.45 (1.0)-30 AA/70 AMD/349 ppm MBA-130 nm 36.7 13.60 (30)-Starch 0 (0) 1.36 (3.0)-Silica-5 nm 46.3 The addition of 6.80 kg/907 kg (15 lbs/ton) of starch, 2.27 kg/907 kg (5 lbs/ton) of Alum and 1.36 kg/907 kg (3.0 lbs/ton) of silica reduces the drainage time 67.7%, however replacement of the silica with 0.45 kg/907 kg (1.0 lb/ton) of organic anionic microbeads reduces the drainage time 69.2% which is slightly better than the silica system with far less added material. EXAMPLE 32 The polymeric, anionic microbead and the silica starch systems of Example 31 are compared for first pass retention values using the alkaline paper stock of Example 2. The results are shown in Table XXXII, below. Cationic Potato Starch Alum Anionic Microparticle First Pass Retention% kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 0 (0) 25 % 6.80 (15)-Starch 0 (0) 1.36 (3.0)-Silica-5 nm 31.7% 6.80 (15)-Starch 1.13 (2.5) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 37.4 % 6.80 (15)-Starch 1.13 (2.5) 0.45 (1.0)-30 AA/70 AMD/349 ppm MBA-130 nm 46.6% The retention values of starch and 1.36 kg/907 kg (3.0 lbs/ton) of silica are surpassed by replacing the silica with 1.13 kg/907 kg (2.5 lbs/ton) alum and either 0.22 kg/907 kg (0.5 lb/ton) of microbead or 0.45 kg/907 kg (1.0 lb/ton) of microbeads. The process of the instant invention results in a 15.25% and a 34.1% improvement in retention values, respectively, over silica. EXAMPLE 33 Retention values using silica and the organic anionic microbead of Table XXXIII are compared in a pilot Fourdrinier papermaking machine. The paper stock consists of pulp made from 70% hardwood and 30% softwood containing 25% calcium carbonate and 2.27 kg/907 kg (5 lbs/ton) of cationic starch. The cationic potato starch is added immediately before the fan pump. The anionic microbeads and alum are added as in Example 18. Cationic Potato Starch Alum Anionic Microbead Ash Retention % kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 0 (0) 34.4% 9.07 (20) 0 (0) 1.36 (3.0)-Silica-5 nm 49.2% 9.07 (20) 2.27 (5.0) 1.36 (3.0)-Silica-5 nm 66.3% 9.07 (20) 2.27 (5.0) 0.45 (1.0)-30 AA/70 AMD/349 ppm MBA-150 nm SV-1.32 68.7% Alum improves the retention values of silica and the alum/silica system retention of 66.3% is slightly less than that of the alum/organic anionic microbead system of 68.7% (3.5% improvement) with 1/3 the concentration of microbead. EXAMPLE 34 A comparison of drainage times between the anionic, organic, microbead system and the silica system is made using the paper stock described in Example 13. It is noted that this stock contains 7.25 kg/907 kg (16 lbs/ton) of cationic potato starch and 2.72 kg/907 kg (6 lbs/ton) of alum. The additives of the Table XXXIV are added in successive runs. Cationic Potato Starch Alum Anionic Microparticle Drainage Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0.80 (15) 0 (0) 1.36 (3.0)-Silica-5 nm 42.5 0.80 (15 ) 0 (0) 1.36 (3.0)-Silica-5 nm 55.6 0.80 (15) 1.13 (2.5) 0.45 (1.0)-30 AA/70 AMD/349 ppm MBA-130 nm 28.7 The silica/starch system is inferior in drainage time to that of the organic microbead system (0.45 kg (1.0 lb) and 1.13 kg (2.5 lbs) alum). EXAMPLE 35 With the same stock as in Example 34, organic, anionic, microbead and silica systems, using a anionic polymer added to the furnish, are compared as to drainage times as in said Example. Alum and cationic starch are added where indicated and the furnish is stirred at 800 r.p.m. for 30 seconds. The anionic acrylamide copolymers and, if added, silica or microbeads are added together to the furnish and stirred for a further 30 seconds at 800 r.p.m. before the drainage rate is measured. See Table XXXV. Anionic Polymer Retention Aid Alum Anionic Microbead Drainage Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 0 (0) 92.4 0.13 (0.3)-30 AA/70 AMD 0 (0) 0 (0) 62.1 0.13 (0.3)-30 AA/70 AMD 2.27 (5.0) 0 (0) 59.4 0.13 (0.3)-30 AA/70 AMD 0 (0) 0.22 (0.5)-Silica-5 nm 50.4 0.13 (0.3)-30 AA/70 AMD 0 (0) 0.45 (1.0)-Silica-5 nm 47.5 0.13 (0.3)-30 AA/70 AMD 2.27 (5.0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 42.2 0.13 (0.3)-30 AA/70 AMD and 10 additional cationic starch 0 (0) 0.45 (1.0)-Silica-5 nm 41.3 0.13 (0.3)-30 AA/70 AMD and 10 additional cationic starch 2.27 (5.0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 28.4 Silica improves drainage times when compared to the anionic acrylamide polymer alone; however, the anionic organic microbeads, in replacing the silica, give even better drainage times with alum. Additional cationic potato starch in the furnish allows the microbead system to produce even faster drainage times. EXAMPLE 36 Comparative retention values are determined for an organic anionic microbead versus a silica system using an anionic polymer and the paper stock of Example 13. The additives, as specified in Table XXXVI, are added as in Example 35. Anionic Polymer Alum Anionic Microbead First Pass Retention% kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0.13 (0.3)-30 AA/70 AMD 0 (0) 0 (0) 34.3 0.13 (0.3)-30 AA/70 AMD 2.27 (5.0) 0 (0) 37.3 0.13 (0.3)-30 AA/70 AMD 0 (0) 0.45 (1.0)-Silica-5 nm 34.0 0.13 (0.3)-30 AA/70 AMD 0 (0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 40.3 0.13 (0.3)-30 AA/70 AMD 2.27 (5.0) 0.22 (0.5)-30 AA/70 AMD/349 ppm MBA-130 nm 52.6 Retention values with 0.13 kg/907 kg (0.3 lb/ton) of anionic polymer, with and without silica, are identical at 34% and addition of 2.27 kg/907 kg (5.0 lbs/ton) of alum and no silica actually increases retention to 37.3%. Anionic polymers, in combination with organic anionic microbeads however, give better retention values without (40.3%) and with alum (52.6%) when compared to the silica system (34%). This retention when combined with the faster drainage rates of the organic anionic microbeads shown in Table XXXV, makes them preferable to either the silica or bentonite systems usually used commercially. EXAMPLE 37 The effect of cationic organic, microbeads is now examined. To an alkaline furnish containing 25% calcium carbonate, 6.80 kg (15 lbs) of cationic starch and 2.27 kg (5 lbs) of alum and of a pH of 8.0, the ingredients of Table XXXVII are added. The anionic polymer is added first and the cationic, organic microbead is added second. Anionic Polymer (Linear) Cationic Microbead or Polymer Drainage Seconds kg/907 kg (lbs/Ton) kg/907 kg (lbs/Ton) 0 (0) 0 (0) 142.7 0.22 (0.5)-30 AA/70 AMD 0 (0) 118.5 0.22 (0.5)-30 AA/70 AMD 0.22 (0.5)-40 AETMAC/60 AMD/100 ppm MBA-100 nm 93.3 0.22 (0.5)-30 AA/70 AMD 0.22 (0.5)-40 AETMAC/60 AMD/100 ppm MBA-1000 nm 113.9 0.22 (0.5)-30 AA/70 AMD 0.22 (0.5)-40 AETMAC/60 AMD/linear Polymer (not a microbead) 98.7 The addition of 0.22 kg/907 kg (0.5 lb/ton) of cross-linked cationic microbead - 100 nm results a drainage time reduction of 25.2%. Addition of 0.22 kg/907 kg (0.5 lb/ton) of linear cationic polymer causes a drainage time reduction but is not as effective as the cationic microbeads of the present invention. EXAMPLE 38 To an acid paper stock made from 2/3 chemical pulp, 1/3 ground wood fiber and 15% clay are added 20 lbs/ton of alum. Half the stock is adjusted to pH 4.5 and remainder is adjusted to pH 5.5. The ingredients shown in Table XXXVIII are added in the same order as Example 37. Examples 39-45 Following the procedure of Example 2, various microbeads, high molecular weight (HMN) polymers and polysaccharides are added to paper-making stock as described therein. In each instance, similar results are observed. Example No. Microbead Polysaccharide HMW Polymer 39 AM/MAA (50/50) Cationic Guar AM/DADM (70/30) 40 AM/VSA (65/35) -- Mannich PAM 41 Mannich PAM CMC AM/AA (80/20) 42 AM/DADM (75/25) -- PAA 43 P(DMAEA) -- -- 44 P(AA) Cationic Guar AM/DMAEA 45 AM/AA (25/75) Cationic Guar AM/AA (70/30) AM = Acrylamide MAA = Methacrylic acid VSA = Vinyl Sulfonic acid DADM = Diallydimethylammonium chloride (AA) = Polyacrylic acid P(DMAEA) = Poly(dimethylaminoethylacrylate) quaternary CMC = Carboxymethyl cellulose Mannich = Polyacrylamide reacted with formaldehyde and PAM diemthyl amine

Claims: A method of making paper which comprises adding to an aqueous paper furnish ionic, organic, polymeric microbeads, characterized in that the ionic, organic, polymeric microbeads a) are added to the aqueous paper furnish in an amount of from 0.02 to 9.07 kg/907 kg (0.05 to 20 lbs/ton), based on the dry weight of the paper furnish solids, b) have an unswollen particle diameter of less than 750 nanometers if cross-linked and less than 60 nanometers if non-cross-linked and water-insoluble, and c) have an ionicity of at least 1%, but at least 5% if cross linked, anionic and used as the sole retention additive. The method according to Claim 1 wherein from 0.02 to 9.07 kg/907 kg (0.05 to 20 lbs/ton), same basis, of a high molecular weight, ionic polymer is added to said furnish in conjunction with said microbeads. The method according to Claim 1 wherein from 0.45 to 22.68 kg/907 kg (1.0 to 50 lbs/ton), same basis, of an ionic polysaccharide is added to said furnish in conjunction with said microbeads. The method according to Claim 1 wherein from 0.04 to 9.07 kg (0.1 to 20 pounds) of an active, soluble aluminum species is also added per 907 kg (ton) of paper furnish solids to the furnish. A composition for the use in papermaking comprising a mixture of A) ionic, organic, polymer microbeads having an unswollen particle diameter of less than 750 nanometers if cross-linked and less than 60 nanometers if non-cross-linked and water-insoluble, the ionicity of the microbeads being at least 1% and either B) a high molecular weight ionic polymer, the ratio of A:B ranging from 1:400 to 400:1, respectively, or C) a ionic polysaccharide, the ratio of A:C ranging from 20:1 to 1:1000, or B and C together, the ratio of A:B and C together ranging from 400:1 to 1:1000.

Inventors: HARRIS ELIETH W, HONIG DAN S, HARRIS, ELIETH W., HONIG, DAN S.
Applicants: CYTEC TECH CORP, CYTEC TECHNOLOGY CORP.
Application year: 1991
Main classification: D21H21
IPC codes: D21H21, C08F226, D21H17, C08F220, C08F20, C08F26, D21H19