MXPA00010903A

MXPA00010903A - Aqueous systems comprising an ionic polymer and a viscosity promoter

Info

Publication number: MXPA00010903A
Application number: MXPA/A/2000/010903A
Authority: MX
Inventors: L Burdick Charles
Original assignee: Hercules Incorporated
Priority date: 1998-05-12
Filing date: 2000-11-07
Publication date: 2001-07-31

Abstract

Aqueous compositions having advantageous rheological properties, preferably including any of enhanced yield stress, enhanced viscosity, and/or enhanced water retention, are disclosed. Included are low-viscosity compositions having high yield stress. The present invention also relates to processes for preparing and using the compositions. Compositions of the present invention comprise aqueous compositions of a polymer having a net ionic charge, and a viscosity promoter having an opposite net ionic charge. Compositions may also comprise a moderating agent to prevent precipitation and/or gelation.

Description

AQUEOUS SYSTEMS THAT COMPRISE AN IONIC POLYMER AND A PROMOTER OF VISCOSITY, PROCEDURES FOR ITS PREPARATION, AND USES OF THE SAME CROSS REFERENCE TO RELATED REQUESTS This application claims priority based on the Request Provisional North American No. 60/086, 0 8, presented the day May 12, 1998, which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION This invention relates to compositions having beneficial rheological properties comprising an ionic polymer and a viscosity promoter. The invention also relates to methods for preparing and using compositions having useful rheological properties, and also relates to compositions and methods for treating paper. BACKGROUND OF THE INVENTION Several industries wish to employ rheology modifiers to achieve thickening, flow control, water retention and other properties in aqueous systems. Numerous rheology modifiers are commercially available such as sodium carboxymethylcellulose, guar gum, sodium alginate, hydroxyethylcellulose, alkali soluble crosslinks, xanthan gum, polyacrylamide, etc. Hydrophilic groups expressing these various water-soluble polymers can be classified as non-ionic, anionic, or cationic. Polymers soluble in ammonium or cationic waters are most commonly used in the absence of an oppositely charged polymer species, due to incompatibility problems. For example, in cases where anionic polymers are used such as paper coating, these polymers are traditionally employed without the use of a cationic additive present, since cationic additives typically precipitate most of the water-soluble ammonia and polymers. therefore they reduce their effectiveness. Similarly, the vast majority of polymers in commercial use, whether anionic or cationic, avoid the use of these additives with oppositely charged species. It is also known that the presence of polyvalent cationic inorganic salts, such as for example calcium or aluminum salts, can adversely affect the solubility and effectiveness of the ammonium polymers. However, even though the presence of polyvalent cationic solutes is usually avoided in applications in which anionic water-soluble polymers are used, occasional findings have been disclosed where an anionic polymer has been employed with cationic polymers soluble in water or with salts inorganic cationic These findings include the following: USP 3.0 9, < J69 presents the use of polymers water-soluble anionics of sodium carboxymethylcellulose in combination with a cationic polyamide-epichlorohydrin polymer to increase paper strength. U.S. Patent Nos. 5,502,091, 5,318,669, and 5,338, 07, disclose mixtures of anionic and cationic guar to increase strength in the dry state of paper. U.S. Patent No. 5,338, 06 and members of the family EP 0362770 disclose high molecular weight cationic water soluble polymer mixtures such as cationic guar or cationic polyacrylamide with anionic polymers to increase paper strength in the dry state. USP 3,719,503 describes the formation of water-based gels through specific mixtures of water-soluble anionic polymers with ammonium salts. USP 4, 035, 195 discloses the use of sodium carboxymethylhydroxyethylcellulose and cationic crosslinking additives such as, for example, chromium or aluminum salts, for the purpose of thickening brine solutions for applications in petroleum fields. In most cases, as for example in US Patent Nos. 3,0 9, 69, 3,058,873, 3,719,503, 5,502,091, 5,318,669, 5,338, 07, and 5,338, 06, ammonium and cationic polymers are mixed in sequence with colloids. , such as paper fibers or particles suspended, in order to facilitate the adsorption / flocculation of the colloids with the water-soluble polymers. Accordingly, the water-soluble polymers are completely removed from the aqueous phase and an increased viscosity of the polymer solution in solution is not obtained. SUMMARY OF THE INVENTION The present invention relates to aqueous compositions having beneficial rheological properties, preferably including any of the following: improved transfer point resistance, increased viscosity, increased water retention, and combinations thereof. The present invention also relates to methods for preparing and using the compositions. The compositions of the present invention can be prepared with an interactive mixture of ionic water-soluble polymer combined in solution with viscosity promoter for the ionic polymer, the viscosity promoter having a net ionic charge opposite to the charge of the ionic polymer. The compositions of the present invention optionally comprise a moderating agent to prevent or reduce the formation of precipitate and / or gel formation. The aqueous solutions of the present invention exhibit unexpected rheological properties and are useful in various applications such as surface treatment of paper sizing press and rheology control of paper coating. The paper sizing press treatment process is commonly used to coat paper. In this process, a previously formed sheet is fed through the size press, where a solution of dissolved starch is typically applied on one or both sides of the paper, typically adding about 3-5% by weight of solids to the paper in dry weight of untreated paper. The paper sheets are typically very absorbent, causing a significant penetration of the starch solution into the pores of the paper. This penetration is undesirable since the coating is typically required on the surface of the paper, not in the pores. Thus, the penetration of the solution requires the addition of more starch to obtain the desired coating, resulting in a loss of efficiency. Although mixtures of anionic guar with cationic guar as well as mixtures of anionic polyacrylamide copolymers with cationic polyacrylamide copolymers have been employed for various purposes in the papermaking art, these compositions are not operative in the present invention due to a strong precipitate formation. Accordingly, the present invention differs in its type from the compositions of the prior art with regard to to the chemical nature of the combined polymer species. The present invention also differs from the prior art in terms of the ratios and concentrations employed to prepare solutions of a novel rheological mixture. The novelty of the present invention is evident recognizing that the prior art in many cases precludes successful mixtures of ammonium polymers and cationic viscosity promoters. In the papermaking industry, there is a need for compositions and methods that can better prevent a coating composition from penetrating deeply into the pores of the paper, thus increasing the coating efficiency. Said efficiency is desirable because it reduces, among other things, the amount of additives, i.e., reinforcing agents and sizing agents that are required. There is also a need for compositions and methods that can effectively seal the pores in the paper, resulting in a paper with reduced porosity. In one aspect, the present invention provides aqueous compositions comprising at least a first ionic polymer and at least one viscosity promoter, the at least one viscosity promoter comprising at least one second ionic polymer having a net ionic charge. opposite to the ionic charge of said at least one first ionic polymer, the aqueous composition has a yield point strength greater than about 5 dynes / cm 2. In another aspect, the invention features an aqueous composition prepared by the combination of at least one ionic first polymer, at least one viscosity promoter, and an aqueous medium, the at least one viscosity promoter comprising at least one second ionic polymer having a net ionic charge opposite the charge of said first ionic polymer, the aqueous composition has a resistance to yield point greater than about 5 dynes / cm2. In another aspect, the invention provides an aqueous composition comprising water, at least a first ionic polymer and at least one viscosity promoter, the at least one viscosity promoter comprising at least one second ionic polymer having a charge net ionic opposite to the ionic charge of the at least one first ionic polymer, the aqueous composition has a yield point resistance of at least about 10% greater than the yield point resistance of a composition having approximately the same viscosity as the aqueous composition, and the same ingredients as said aqueous composition but without at least one of the at least one first ionic polymer or at least one viscosity promoter. In another aspect, the invention provides an aqueous composition comprising water, at least one first ionic polymer and at least one viscosity promoter, the at least one viscosity promoter comprises at least one second ionic polymer having a net ionic charge opposite to the charge of the at least one first ionic polymer, the aqueous composition has a higher viscosity than the viscosity of a composition having the same ingredients and ingredient concentrations as the aqueous composition but without any of the at least one ionic first polymer or the at least one viscosity promoter, where the concentration of an ingredient is measured as a percentage by weight based on total weight. In another aspect, the invention provides an aqueous composition comprising at least one ionic polymer, at least one viscosity promoter and at least one moderation agent, the at least one ionic polymer has a net ionic charge opposite to the loading of the at least one viscosity promoter, the at least one moderating agent is present in an effective amount to prevent the formation of a precipitate or gel, the precipitate or gel comprises an interactive complex of the at least one first polymer ionic and at least one viscosity promoter. In another aspect, the present invention provides a method for coating a porous surface, the method comprising applying to the surface an aqueous composition which , * '_. it comprises at least one first ion polymer and at least one viscosity promoter, the at least one ionic polymer having a net ionic charge opposite to the charge of the at least one viscosity promoter. In another aspect, the present invention provides a method for the surface sizing of paper, which comprises the use of any of the compositions of the invention, as well as paper, preferably sized paper, coated by the compositions and / or methods. A preferred method comprises: a) supplying paper; b) applying an aqueous composition in accordance with the present invention on at least one surface of the paper; and c) drying the paper to obtain a paper with surface sizing. In another aspect, the present invention offers a method for reducing the porosity of a porous surface, preferably a fibrous sheet, more preferably paper, comprising the application of a composition of the invention on the porous surface. The invention also includes porous surfaces, fibrous sheets, and paper coated by methods and / or compositions of the present invention. The aqueous compositions preferably have transfer point strengths greater than about 5 dynes / cm 2, more preferably greater than about 10 dynes / cm 2, more preferably greater than about 20 dynes / cm 2, with greater preference greater than about 30 dynes / cm2, more preferably greater than about 50 dynes / cm2, and preferably even greater than about 70 dynes / cm2. In addition, the aqueous compositions preferably have at least about 10% higher yield strengths, preferably at least about 50% higher, more preferably at least about 100% higher, and preferably even higher. at least about 200% greater than the yield point strength of a composition having approximately the same viscosity as the aqueous composition, and the same ingredients as said aqueous composition but without at least one of the at least one first ionic polymer and at least one viscosity promoter. The Brookfield viscosities of the aqueous compositions are preferably less than about 10,000 cps, more preferably less than about 5,000 cps, more preferably less than about 1,000 cps, more preferably less than about 500 cps, preferably even less than about 300 cps, and may be less than about 200 cps or less than about 100 cps. The Brookfield viscosities are preferably greater than about 50 cps.

The compositions of the present invention preferably include any of solutions, microemulsions, emulsions, dispersions and suspensions. The at least one first ionic polymer preferably has a net anionic charge, and preferably comprises at least one anionic polysaccharide, anionic polysaccharide derivative, synthetic anionic polymer or combinations thereof. The first preferred ionic polymers which are derivatives of ammonium polysaccharides include carboxy ethylcellulose, sodium carboxymethylcellulose, carboxymethylguar, carboxymethylhydroxypropylguar, carboxymethylhydroxyethylcellulose, sodium carboxymethylhydroxyethylcellulose, methylcarboxymethylcellulose, carboxymethyl starch, sodium alginate, alkali soluble latex, and combinations thereof. The first preferred ionic polymers which are synthetic anionic polymers include anionic acrylamide copolymer, amphoteric acrylamide copolymer, polyacrylic acid, acrylic acid copolymer, and combinations thereof. Preferably, a solution having 10% by weight or less of the at least one first ionic polymer in water has a Brookfield viscosity at room temperature greater than approximately 1,000 cps. The at least one viscosity promoter preferably includes at least one second ionic polymer, at least one salt having a polyvalent cationic functionality, and combinations thereof. The compositions of the present invention may include the at least one salt in addition to the at least one second ionic polymer. Preferably, the at least one second ionic polymer comprises at least one cationic polyacrylamide; a reaction product of polyaminoamide aiohydrin obtained by reaction of polyamines with dicarboxylic acids; diallyl dimethyl ammonium chloride polymer, hlorohydrin ida polyester polymer, quaternary monomer polymerization product, quaternary monomer copolymers with other reactive monomers, adduct of quaternary epoxides with water soluble polymers, hlorohydrin reaction product of a polyaminoamide obtained by reaction of adipic acid with diethylenetriamine, and combinations thereof. Preferably, a solution having 5% by weight of the at least one second ionic polymer in water has a Brookfield viscosity at room temperature less than about 2,000 cps. The at least one salt having a polyvalent functionality, which is preferably cationic, includes preference divalent or trivalent functionalities, or combinations thereof. A preferred salt is an inorganic salt, preferably comprising at least one multivalent metal cation, and preferably comprising a salt of at least one of the following: aluminum, magnesium, iron III, calcium, zinc, and combinations thereof. The charge density of the at least one first ion polymer is preferably at least about 0.5 meq / gram. The charge density of the at least one viscosity promoter is preferably at least about 0. meq / gram. The charge ratio between the at least one first ion polymer and the at least one viscosity promoter is preferably greater than 1: 1, more preferably greater than about 1: 0.6, more preferably greater than about 1: 0. . , more preferably greater than about 1: 0.3, preferably even greater, greater than about 1: 0.2, and with special preference greater than about 1: 0.1. The compositions may include at least one moderating agent present in an amount effective to prevent the formation of a precipitate or gel, the precipitate or gel comprises an interactive complex of the at least one first ionic polymer and the at least one viscosity promoter. , said precipitate or gel would be formed in the absence of the - **! ££ -: - moderation. Preferably, the at least one moderating agent comprises at least one inorganic salt having a divalent cationic functionality, a carboxylic acid salt, a starch solution, and combinations thereof. The aqueous composition of the present invention preferably has a gravimetric water retention value that is less, preferably at least about 10% less than a composition having the same ingredients in the same concentrations but without any of said at least a first ionic polymer and said at least one second ionic polymer. The compositions and methods according to the present invention include additives. Preferred additives include sizing agents; natural, semi-synthetic or synthetic polymers, latex colloids; pigments; clays; fillers; biocides; surfactants; antistatic agents; foam anti-foaming agents; binders (e.g. latex binders; retention aids; reinforcing agents; and combinations thereof).

Preferred sizing agents include sizing agents reactive with cellulose. Preferred sizing agents include alkylketone dimers, alkylketone multimers, succinic acid anhydrides, styrene maleic anhydrides, maleic anhydride copolymers styrene, starches, hydrophobic latex polymers, organic epoxides, acyl halides, fatty acid anhydrides, organic isocyanates, and combinations thereof. A paper sized in accordance with the present invention preferably has a higher level of sizing as measured by the Hercules sizing test than a paper sized with a surface sizing composition that is the same but without at least one promoter of viscosity. Preferably, a coated and / or sized paper employing a composition of the present invention has a Gurley porosity higher than a paper sized with a surface sizing composition that is the same except that it has at least one viscosity promoter . Preferred compositions of the present invention are any of the paper coating compositions, paper sizing compositions, paints (e.g., latex paints), oil field drilling muds, oil field fracturing fluids, compositions of water purification, and retention aids. As noted, the present invention includes the above compositions and methods, as well as preparation of the compositions, use of the compositions, and products prepared using compositions and / or methods of the present invention. invention. DETAILED DESCRIPTION OF THE INVENTION Unless stated otherwise, all percentages, parts, proportions, etc., are offered by weight. By "room temperature" we mean a temperature of approximately 25 ° C. Unless stated otherwise, a reference to a compound or component includes the compound or component itself as well as in combination with other compounds or components as well as mixtures of compounds. Further, when a quantity, concentration or other value or parameter is provided as a list of preferable upper values and preferable lower values, it will be understood that all ranges formed from any pair of a preferred upper value and a value are specifically presented. lower preferred, regardless of whether the ranges are disclosed separately. In addition, unless otherwise stated, the term "anionic polymer," as used herein, refers to polymers having a net anionic charge and including amphoteric polymers having a net anionic charge. Similarly, unless otherwise stated, the term cationic polymer, as used herein, refers to polymers having a net cationic charge, and therefore include amphoteric polymers that have a charge net cationic The yield point resistance is measured here with an AR1000 rheometer (TA Instruments, Newcastle, DE) using the flow test at 0.2 sec cut speeds "1 to 288 sec" 1. For aqueous compositions that do not include a starch or starch derivative, the yield point strength is measured at a temperature of 25 ° C. In the case of aqueous compositions that include a starch or starch derivative, the yield point strength is measured at 65 ° C. The sample vessels used are the double-spaced rocker and cup tools. There is an opening of 3 mm between the two cylinders of the tools. Approximately 8 ml of the test composition is placed in the cup, a cap device is placed over the filled rocker and cup assembly to minimize evaporation of the fluid during the test, and the test begins. The instrument measures the cutting effort as the cutting speed is raised from low settings to high settings. The data is then analyzed using the Casson model, and the yield point resistance of the sample is obtained in this way. One of the modifiable rheological properties of the present invention is the viscosity. There are many methods to measure viscosity, and the methods usually used vary by industry. When comparing viscosities of compositions (such as by ratios or percentage increases or decreases) any measurement method and viscosity is appropriate insofar as the determinations are made in the same way and in the same conditions for all the compositions to be compared. Such methods include, but are not limited to, Brookfield viscosity and Stormer viscosity. As used herein for compositions having defined Brookfield viscosities, viscosities are measured with an LVT viscometer using a spindle speed of 12 revolutions per minute. In the case of compositions that do not include starch or starch derivative, the viscosity is measured at a temperature of about 25 ° C. In the case of compositions that include a starch or starch derivative, the viscosity is measured at a temperature of about 60 ° -70 ° C, for example, 65CC. In the case of viscosities in the range of approximately 0-450 cps, a No. 1 spindle is used, in the case of viscosities within the range of approximately 450-2,250 cps, a spindle No. 2 is used, for viscosities within a range of about 2.2 50-9,000 cps, a No. 3 spindle is employed, and in the case of viscosities within a range of about 9,000-45,000 cps, a No. 4 spindle is employed. pigmented paper, viscosities can be measured using an RVT viscometer and a spindle speed of 100 revolutions per minute, at a temperature of approximately 25 ° C. In the case of viscosities within a range of approximately 0-1,800 cps, a No. 4 spindle is employed. In the case of viscosities within a range of approximately 1,800 to 3,600 cps, a No. 5 spindle is employed, and in In the case of viscosities within a range of approximately 3,600 to 9,000 cps, spindle No. 6 is employed. Scientific literature teaches that the penetration rate of aqueous solutions in porous substrates should be the same for solutions of similar viscosity. However, it has now been found that solutions of the present invention, mixtures of water-soluble ionic polymers with viscosity modifiers, present a significantly lower penetration of the mixture into a substrate with absorption capacity compared to control solutions with equivalent viscosities. . The equations that describe the rate of absorption of solutions in porous media are published in the scientific literature, including the Lucas-Washburn equations and Darcy's law. Darcy's law is approximated by the following expression: KP Vo o (1)? where Vo is the absorbance speed of the solution in a porous substrate, K is the permeability of the surface, P is an applied pressure term, and? It is the viscosity of the solution. While this equation is adequate in the case of Neonian fluids, it is suggested that this equation does not adequately describe the behavior of polymer solutions.

In many industrial processes and applications, a modifier is added to the water or to another aqueous liquid in order to control the rheological properties and consequently obtain useful flow properties. A rheological property of this type is the "yielding point strain" which is the critical effort, or cutting speed, which must be exceeded so that some non-Newtonian fluids flow. The yield point resistance is related to the ability of a solution to act as a suspension aid. The yield point resistance of a composition is an intrinsic property of the composition. The yield point resistance is therefore independent of the nature of a surface or container in contact with the composition. In equation 1, the pressure term P can, in static situations, be equivalent to capillary pressure. Thus, P depends on various factors such as pore size of the surface, and the humidification capacity, or contact angle, between the fluid and the surface. Thus, P is not an intrinsic property of the fluid but depends on the properties of the surface and the fluid as well as the interactions between the surface and the fluid. Without being limited by any theory, it is considered that the ceding point deformation of a composition, although it is an intrinsic property of the composition, also refers to the speed of absorption of the fluid on a surface. It is believed that the yield point strain effectively reduces the applied pressure, P, in equation 1, thus reducing the rate of absorption. Thus, the yield point deformation can be a variable that influences the resistance properties of a solution of polymers, for example starch solutions, in contact with porous surfaces, for example paper. The present invention includes compositions comprising an aqueous solution comprising a first ionic polymer and a viscosity promoter. The compositions may have high yield strength in low viscosity. The yield point resistance is measured in accordance with the procedure presented in the examples section below. Preferred compositions of the present invention have yield point strength values of at least about 5 dynes / cm 2, more preferably at least about 10 dynes / cm 2, preferably even higher at least about 20 dynes / cm 2, with still greater preference at least SS £ 2. & * about 30 dynes / cm.sup.2, preferably even more at least about 50 dynes / cm.sup.2, and especially at least about 70 dynes / cm.sup.2. Although there is no specifically desired upper limit as to the yield point resistance of a solution of the present invention, the yield point strength will preferably be less than about 100 dynes / cm 2. Compositions of the present invention exhibit increased yield point strengths compared to compositions that do not have the first ionic polymer or the viscosity promoter. Compositions of the present invention comprise a moderation agent that further exhibits increased resistance to yield point compared to compositions that do not have the moderation agent. The yield point resistance of a composition of the present invention is preferably at least about 10% greater than the yield point resistance of a composition having the same viscosity and ingredients but without at least one of the first ionic polymer or promoter of viscosity, more preferably, at least about 50% higher, preferably even higher, at least about 100% higher, and especially at least about 200% higher. The viscosities of the solutions of the present invention are preferably such that the solutions can be emptied and pump. The Brookfield viscosities are measured in accordance with the procedure set forth in the examples section below. The Brookfield viscosity of an ionic polymer / viscosity promoter solution according to the present invention is preferably less than about 10,000 cps, more preferably less than about 5,000 cps, preferably even more, less than about 2,000 cps, with even greater preference less than about 1,000 cps, preferably even more less than about 500 cps, preferably even more less than about 300 cps, and may be added at a level down to less than about 200 cps, or even less than about 100 cps . The viscosity of the solution is preferably greater than about 50 cps, more preferably greater than about 100 cps. Accordingly, preferred ranges of viscosities include from about 50 cps to 10,000 cps, more preferably from about 50 cps to 5,000 cps, preferably even greater than about 50 cps to 1,000 cps, preferably even greater than about 50 cps to 500 cps. , and especially from approximately 100 cps to 300 cps. Compositions of the present invention include aqueous solutions comprising a first ionic polymer and a viscosity promoter. The first ionic polymer and the The viscosity promoter can form an interactive complex of molecular weight high enough to act non-neatly. Preferably, a high molecular weight interactive complex is obtained with one or both of the first ionic polymer and viscosity promoter comprising a high polymer, i.e., a polymer having a high molecular weight. Preferably, the first ionic polymer is of high molecular weight. The combination of the first ionic polymer and the viscosity promoter forms a true interactive complex solution in an aqueous medium, such as water. The viscosity of the formed solution is greater than the solution of the first ionic polymer or the viscosity promoter, individually. In other words, the viscosity of the solution formed is greater than the viscosity of a solution containing the same amounts of the same ingredients, but without the first ionic polymer or the viscosity promoter. As indicated above, either the first ion polymer or the viscosity promoter or both the first ion polymer and the viscosity promoter is / are preferably a polymer with high molecular weight. By high molecular weight we mean a polymer that preferably has a sufficiently high molecular weight such that a solution having 10% by weight or less of the The polymer in water produces a Brookfield viscosity at room temperature greater than about 1000 cps. Although there is no preferred upper limit in terms of the molecular weight of a high polymer, a solution having 1% by weight or less of a high polymer in water preferably produces a Brookfield viscosity less than about 10,000 cps. According to the needs of the application, the first ionic polymer can be anionic, amphoteric, or cationic, insofar as it has a net ionic charge. The first ionic polymer is preferably anionic or amphoteric, preferably has a net anionic charge, and is preferably anionic. The first ionic polymer is water soluble, this means that the polymer can form a non-colloidal 1% by weight aqueous solution at room temperature (about 25 ° C). The degree of ion substitution can be determined based on the known structure of a polymer by the equation: ion substitution (meq / g) = 1000 (2) I molecular weight per charge | The ionic substitution can also be determined experimentally, for example, by the use of colloidal titration techniques. The degree of ionic substitution of the first ionic polymer that is preferably anionic, is preferably at least about 0.04 meq / g, more preferably at least about 0.5 meq / g, preferably even higher at least about 0.1 meq / g, preferably still at least at least about 1 meq / g, especially at least about 3 meq / g. The degree of ion substitution is preferably less than about 10 meq / g, more preferably less than about 5 meq / g, and still preferably less than about 4 meq / g. Ionic polymers which can be selected as the first ionic polymer are preferably anionic and preferably have a high molecular weight. Thus in a preferred aspect, soluble polymers anionic water in combination with promoters cationic viscosity produce a yield strength enhanced significantly and / or water retention significantly enhanced in a solution viscosity given in comparison with the polymers of control without cationic viscosity promoters present. Thus, in a particular embodiment, the invention comprises a preferably aqueous solution of 1) as the first ionic polymer, a high molecular weight anionic water soluble polymer and; 2) as a viscosity promoter, a polyvalent cationic additive such as, for example, a high-density water-soluble polymer, or an inorganic additive cationic, such as calcium or aluminum salt. Soluble polymers anionic water in accordance with the present invention include, without limitation, sodium carboxymethylcellulose, carboxymethyl 5 sodium, pectin, carrageenan, carboxymethylguar gum, sodium alginate, copolymers of anionic polyacrylamide, soluble latex alkalis, carboximetilmetilcelulosa, carboxymethyl idroxipropilguar, and other anionic carbohydrate derivatives as well as mixtures that include one or several of these polymers. Preferably, the anionic polymer includes sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose, pectin, carrageenan, carboxymethylguar gum, sodium alginate, anionic polyacrylamide copolymers and alkali-soluble latex, and mixtures that include one or more of these polymers. Commercially available products that can be employed as the first anionic water soluble ionic polymer or as a component thereof include CMC-9M31 (sodium carboxymethylcellulose; Hercules Incorporated), CMHEC 420H (carboxymethyl; Hercules Incorporated), Pectin LM104 AS-Z (anionic pectin; Hercules Incorporated), Carrageenan J (Hercules Incorporated), Galactosol (carboxymethyl gum, Hercules Incorporated), Alcogum L-29 (a soluble latex alkalis Aleo Products), Kelgin MV (sodium alginate; Kelco, San Diego), Retain 215 (anionic polyacrylamide, Hercules Incorporated), and others in accordance with what is indicated in the following examples. Water-soluble cationic polymers in the present invention include, but are not limited to, polymers and copolymers of cationic polyacrylamide; epihaiohydrin reaction products of polyaminoamides obtained by reaction of polyamines with dicarboxylic acids; and polymers of diallyldimethylammonium chloride (DADMAC) as well as mixtures including one or more of these polymers. Among these, Reten 203 (Hercules Incorporated) and Kymene 557H (Hercules Incorporated) are preferred. The combination of the first ionic polymer and viscosity promoter in aqueous solution increases the viscosity and / or yield point resistance compared to a solution where the first ionic polymer or the viscosity promoter is not found. The viscosity promoter preferably comprises a second ionic polymer and / or a polyvalent salt. For example, when the first ionic polymer is an anionic polymer, the cationic additive employed as the viscosity promoter is either a cationic polymer or a polyvalent cationic salt. When the viscosity promoter comprises a second ionic polymer, the second ionic polymer includes an ionic polymer having a net ionic charge opposite to the charge of the first ionic polymer. You can have units of monomers of the same sign as the net charge of the first ionic polymer insofar as the net charge of the second ionic polymer is opposite to the net charge of the first ionic polymer. When the viscosity promoter is a polymer, it may have a high or low molecular weight. If the first ionic polymer is a high molecular weight polymer, preferably a first anionic ionic polymer, then the polymer viscosity promoter is preferably of low molecular weight. By low molecular weight we mean a 5% by weight solution of the polymer in water having a Brookfield viscosity at room temperature of less than about 2,000 cps when measured in accordance with the procedure described above. In the case of the viscosity promoter, a high molecular weight polymer is a polymer that is not a low molecular weight polymer, ie a polymer for which a 5% solution in water has a Brookfield viscosity at higher room temperature that approximately 2,000 cps. A polymer used as a viscosity promoter is preferably highly charged. By this we understand that the degree of charged character of these viscosity promoters is preferably greater than about 0.05 meq / g, more preferably greater than about 0.1 meq / g, with still greater preference, greater than about 1.0. meq / g, and especially, greater than about 3 meq / g. While there is no preferable upper limit as to the degree of chargedness of the polymer viscosity promoter, it is generally less than about 10 meq / g, more preferably less than about 5 meq / g, still more preferably less than about 4 meq / g. / g. The polymers used as viscosity promoters are preferably low molecular weight and highly charged. Water-soluble cationic polymers as viscosity promoters include, but are not limited to, a) cationic polyacrylamide polymers and copolymers; b) epihaiohydrin reaction products of polyaminoamides obtained by reaction of polyamines with dicarboxylic acids; and c) diallyldimethylammonium chloride polymers (DADMAC). Cationic polyacrylamides of type (a) include copolymers of acrylamides or methacrylamide with cationic monomers such as DADMAC, methacryloxyethyltrimethylammonium chloride and acryloxyethyltrimethylammonium chloride. Mixtures that include one or more of these polymers are also included. A preferred cationic polymer of type (b) is Kymene ® 577H available from Hercules Incorporated, Wilmington, DE. Kymene® 577H is the product of the reaction of epichlorohydrin with a polyamidoamide derived by reaction product of adipic acid with diethylenetriamine. A preferred polymer of this type (c) is Reten (R) 203, a poly (DADMAC) available in Hercules Incorporated, Wilmington, DE. Anionic polymers such as viscosity promoters include, but are not limited to, CMHEC, CMC, styrene-maleic anhydride resins (SMA resins), polyacrylates, and copolymers thereof, as well as blends that include one or more of these polymers. Such polyvalents which are useful as viscosity promoters in the present invention include salts having a polyvalent functionality. Thus, the polyvalent functionality can be anionic or cationic according to the nature of the first ionic polymer. Any ion can be used to balance the charge of polyvalent functionality. Salts having a polyvalent cationic functionality, therefore, can be employed as viscosity promoters for a first ionic polymer that is anionic. The fact that cationic functionality is polyvalent means that it has a valence of at least +2. Thus, preferred polyvalent cationic functionalities include functionalities that are divalent, trivalent, tetravalent or greater, preferably divalent or trivalent. Preferably, salts of tetravalent metals, such as for example group IVB transition metals, for example, zirconium, are not included as viscosity promoters. Preferred salts that have functionalities Cationic polyvalents include polyvalent metal salts, including toric alkaline metals, transition metals and group IIA metals. Such salts include aluminum, magnesium, iron III, calcium and zinc salts. Calcium and aluminum salts such as for example aluminum acetate or calcium chloride are preferred. Mixtures that include one or more of these salts, for example, mixtures of two or more of the listed salts can also be used. As indicated, mixtures of viscosity promoters are also within the scope of the invention. Thus, in addition to mixtures of salts or mixtures of second ionic polymers as mentioned above, the viscosity promoter may also comprise a mixture of at least one salt and a second ionic polymer. The first ionic polymer is preferably present in an excess, preferably a large excess relative to the viscosity promoter in terms of charge ratio. To calculate the charge ratio, the ionic substitution of the first ionic polymer (for example, according to that calculated from equation 2, above) is multiplied by its weight to obtain the "total charge" of the first ionic polymer. The same is for the viscosity promoter (either as for example, salt, polymer, or mixture), to obtain the "total charge" of the viscosity promoter. The "charge ratio" is obtained taking the ratio between the total charge of the first ionic polymer and the viscosity promoter. It is preferred that the charge ratio between the first ion polymer and the viscosity promoter be greater than 1: 1, more preferably greater than about 1: 0.6, more preferably greater than about 1: 0.4, more preferably greater than about 1: 0.3, preferably even greater, greater than about 1: 0.2, and especially greater than about 1: 0.1. In general, it is observed that when cationic substances such as alum, Kymene 557H or other cationic agents are mixed with anionic polymers, such as carboxymethylcellulose, a precipitate or gel can be formed. A characteristic of the formation of the precipitate is that the viscosity of the composition decreases. The formation of a gel, in contrast, results in a very high viscosity composition, whose viscosity can not be easily adjusted through, for example, dilution with an aqueous medium. To avoid the formation of a gel and / or precipitate, the ammonium and cationic components can be mixed in the presence of a moderating agent. Thus, the use of a moderation agent results in a solution with increased viscosity and modified rheological properties. Any material that prevents or reduces formation of precipitate and / or gel between a cationic and anionic polymer it can be used as an agent of moderation. Preferred moderation agents are cationic or anionic. Preferred types of moderating agent include inorganic salts having a polyvalent cationic functionality, salts having an anionic functionality, and starch solutions. Preferred cationic moderation agents include inorganic salts having a divalent cationic functionality, and include cationic salts useful as viscosity promoters. Thus, a cationic salt may be capable of acting as a viscosity promoter and as a moderating agent in a composition of the present invention. When a moderating agent comprises a cationic salt of a composition of the present invention, it is preferable that the cationic salt does not act as a viscosity promoter in this composition. Preferred anionic moderation agents include salts having an anionic functionality. Salts having anionic functionality are suitable for use with a first ionic polymer that is anionic or cationic. Said salt is preferably a salt of a polybasic carboxylic acid. Thus, the anionic functionality is preferably carboxylate, of which at least two carboxylate groups are preferably found in the salt, that is, the preferred salts are salts of carboxylic acids. Preferred anionic functionalities include citrates, formats, bicarbonates, maleates, malonates, acetates, oxalates, succinates, etc.

Specific salts that provide anionic functionalities suitable for use in this invention include sodium citrate (eg, trisodium citrate or disodium citrate), potassium citrate, sodium formate, potassium formate, sodium acetate, and sodium, potassium polyacrylates or low viscosity ammonium. Additional moderation agents include starch solutions, preferably hot starch solutions. Without being limited by any theory, even though starches are generally considered to be non-ionic, it is believed that the starch molecules contain certain carboxylate functionalities that provide a slight degree of anionic character to the starch. Accordingly, it is believed that the effectiveness of starch solutions as moderation agents may be due to these carboxylate functionalities. Accordingly, in another aspect of the present invention, there is provided an aqueous composition comprising a solution of a first ionic polymer, a viscosity promoter and a moderation agent. Without wishing to be bound by any theory, it is believed that, in this aspect of the invention, the viscosity promoter moderates the interactions between the ionic polymer and the viscosity promoter, thus preventing precipitation or gel formation that would occur in the absence of the moderation. That is to say, it is believed that the components form an "interactive complex", where Moderation agent ions act as a "buffer" between the ionic polymer and the viscosity promoter. The interactive complex remains soluble in water and has unusual theological properties. Aqueous compositions of the first ionic polymer and viscosity promoter can be prepared by combining the ingredients in any order. Such compositions are preferably prepared by first dissolving an ionic polymer, either anionic or cationic, in water. The mixture is then preferably modified by the addition of a viscosity promoter. Additives, in accordance with what is described in more detail below, may also be employed. When additives are used, they can be added at any stage, to any component. Preferably the additives that combine with the first ionic polymer, preferably in an aqueous medium, before the combination with the viscosity promoter. Aqueous compositions of ionic promoter, viscosity promoter and moderation agent are prepared by adding the moderation agent to either the first ionic polymer or the viscosity promoter, preferably the first ionic polymer, before combining the first ionic polymer and the viscosity promoter. The moderation agent and the ingredient with which it is combined, either the first ionic polymer or the viscosity promoter, can have net ionic charges of the same sign or opposite sign. It is also possible to mix the first ionic polymer with a first moderating agent, the viscosity promoter with a second moderating agent, then combining the solutions obtained in this way. The results of these methods is a modification of the rheological properties compared to a solution containing the same amounts of the same ingredients, but without the ionic polymer, viscosity promoter or moderation agent. Preferably, the rheologically modified composition has an increased viscosity, and / or an increased yield point resistance compared to solutions of the first ionic polymer, viscosity promoter or individual moderation agent. Without wishing to be bound by any theory, it is believed that the formation of an interactive complex increases the yield point resistance of these solutions. The development of a significant solution point-to-yield strength value in a low Brookfield viscosity solution represents a significant challenge in clear contrast to the act of crosslinking a concentrated solution of high Brookfield viscosity polymer to form a gel. Another rheological property that is preferably modified in compositions of the present invention is water retention. For many purposes, such as in papermaking compositions, it is desirable to increase the water retention of a composition to thereby decrease the speed and degree of absorption in the paper. When measured by the gravimetric water retention method (GWR), as for example in accordance with the technique described in the following examples, water retention is provided in units of g / m2, and lower values indicate better retention. The compositions of the present invention exhibit improved water retention compared to comparative compositions that do not have either the first ionic polymer or the viscosity promoter. Thus, compositions of the present invention have lower GWR values than the GWR values of comparative compositions as defined above. The GWR of a composition of the present invention is preferably less than about 0.9 times the GWR of a comparison composition (i.e., at least about 10% less), more preferably less than about 0.8 times (i.e. at least about 20% less), and still more preferably, less than about 0.7 times the GWR of a comparison composition (i.e., at least about 30% less). While there is no lower limit preferable as far as - < Mfc »-« * J to the GWR of the compositions of the invention, the GWR is typically greater than about 0.01 times the GWR of a comparative composition, more typically greater than about 0.0125 times, even more typically greater than about 0.02 times, and still more typically greater than about 0.025 times the GWR of a comparison composition. Thus, preferred ranges for the GWR of the compositions of the present invention include between about 0.9 and about 0.01 times the GWR of a comparison composition, more preferably between about 0.9 and about 0.0125 times the GWR of a comparison composition, preferably even greater between about 0.8 and 0.2 times the GWR of a comparison composition, and still more preferably, between about 0.7 and about 0.025 times the GWR of a comparison composition. Compositions and methods of the present invention are suitable for use in several areas. Such areas include, but are not limited to, surface coating of paper, internal addition of dry strength additives, thickening of latex paint, drilling mud of oil fields, fracturing fluids of oil fields, water purification, as auxiliary retention in applications where high resistance to transfer point is desired, as well as in applications in which it desires a reduction in surface absorption and / or reduced surface porosity. As desired for a particular application, compositions and methods of the present invention may include additives. When additives are used, as is preferred in papermaking, these additives preferably include any combination of sizing agents: natural, semi-synthetic or synthetic polymers (eg, natural or modified starches); pigments; fillers; biocides; surfactants; antistatic agents; antifoam agents; binders (e.g., crosslinkers, proteins, starches); retention agents; and reinforcing agents. The compositions of the present invention may comprise aqueous solutions comprising the first ionic polymer and viscosity promoter itself or including a moderating agent, and may comprise aqueous compositions containing additives. In addition, when the compositions of the present invention incorporate additives, the compositions may be solutions, colloids, (e.g., microemulsions, emulsions and dispersions) or suspensions. Thus, compositions of the present invention may comprise additives, and include aqueous compositions which are solutions, emulsions, dispersions, or suspensions. Such compositions and uses thereof are found within of the scope of the present invention and comprise aqueous compositions of the present invention. Compositions of the present invention can be used to increase the yield point resistance of aqueous compositions. In numerous publications, the case of xanthan gum, a non-ionic polymer, having a significant yield point resistance in dilute aqueous solution has been discussed. It was unexpectedly found that solutions of the present invention, comprising a combination of at least two interactive species, offer higher yield point strengths than xanthan gum with equivalent Brookfield viscosities, for example, in diluted solutions, which indicates that this invention could find widespread use in applications, for example, industrial applications, where increased resistance to yield point is desired. In applications where it is desired to coat a porous surface, the compositions and processes of the present invention can be used to increase the coating efficiency. By increasing the coating efficiency, compositions of the present invention can be used to increase the filler content and / or reduce the amount of coating materials that are employed. In the area of papermaking, for example, the best coating efficiency provided by the present invention can cause a reduced powder formation and can allow a paper production with a reduced content of wood pulp. In papermaking, compositions can be applied in any manner, including externally, as for example by surface application in a size press, and / or internally as for example by the addition of a pulp paste. Preferably, the compositions are applied to the paper externally. The compositions can be applied as a coating for paper in any given amount useful for the particular application. Pigmented surface additives are typically applied in an amount of about 10% to 40% by weight, based on the dry weight of the paper, more preferably from about 20% to 30% by weight, based on the dry weight of the paper. Non-pigmented surface additives, for example, starch additives, are typically applied at a rate of about 3% to 10% by weight, based on the dry weight of the paper, more preferably from about 5% to 8% by weight, with based on the dry weight of the paper. When solutions of the present invention are incorporated with additives, it is expected that the viscosity ranges of these filled systems will be greater than without additives. Viscosities can be determined by any known method by an expert with ordinary knowledge in the technique for the particular application. When manufactured, sold or transported as concentrate, for example, the Brookfield viscosity can be as high as is commercially practical, typically about 10,000 cps or less, such as between 100 and 10,000 cps. When used as starch solutions, for example, in papermaking, Brookfield viscosities are typically within the range of about 50 cps to 300 cps. When the compositions of the present invention are used as pigmented paper coatings, the Brookfield viscosities are typically within the range of about 1,000 to 5,000 cps. When the compositions of the present invention are used in pigmented coatings such as latex-type paints, Stormer viscosities will typically be in the range of about 80 to about 120 krebs. As indicated, the compositions of the present invention may be in the form of concentrates. The concentrates can be subsequently diluted or mixed with additives as necessary. Such concentrates are concentrated in order to reduce, for example, transportation costs and / or storage space. The concentrated form results, inter alia, in a viscosity higher than the composition when it is diluted and ready for use. Do not there is no upper limit in terms of the viscosities of such compositions. For convenience, however, the viscosities are preferably less than about 10,000 cps so that they can be emptied and pumped without specialized equipment. When the compositions or methods of the present invention are employed with a sizing agent, any sizing agent, preferably sizing agents that react with cellulose, may be employed. Preferred cellulosic reactive surfactants include dimeters and multimers of ketene, alkenyl succinic anhydrides, styrene-maleic anhydrides, organic epoxides containing from about 12 to 22 carbon atoms, acyl halides containing from about 12 to 22 carbon atoms, acid anhydrides. fatty acids from fatty acids containing from about 1 to 22 carbon atoms, and organic isocyanates containing from about 12 to 22 carbon atoms. Preferably, the cellulose derivative dressings used in compositions and methods of the present invention comprise alkylethane dimeters, alkylmethyl multimers, and / or alkenyl succinic anhydrides. Mixtures of sizing agents, which preferably include at least one sizing agent reactive with cellulose, are also included in compositions and methods of the present invention.

Ketene dimers and multimers are materials of formula I: where n is an integer from about 0 to about 20; R and R ", which may be the same or different, are straight or branched chain alkyl groups saturated or unsaturated having from 6 to 24 carbon atoms, and R 'is a straight or branched chain alkyl group saturated or unsaturated having from about 2 to about 40 carbon atoms The ketene dimers have the structure of the formula I where n = 0. The ketene dimers suitable for use in the present invention preferably include the ketene dimers in which the groups R and R ", which may be the same or different, are hydrocarbon radicals. Preferably, the groups R and R "are alkyl or alkenyl groups having from 6 to 24 carbon atoms, cycloalkyl groups having at least 6 carbon atoms, preferably having at least 6 carbon atoms, aralkyl having at least 7 carbon atoms, alkaryl having at least 7 carbon atoms, and mixtures thereof. More preferably, the ketene dimer is selected from the group consisting of (a) octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, β-naphthyl, and cyclohexyl-buttene dimers, and (b) ketene dimers prepared from organic acids selected from the group consisting of montanic acid, naphthenic acid, 9,10-decylenic acid, 9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, acid linoleic, eleostearic acid, naturally occurring mixtures of fatty acids found in coconut oil, babassu oil, palm oil, olive oil, peanut oil, rapeseed oil, beef bait, bacon, whale fat, and mixtures of any of the aforementioned fatty acids between them. More preferably, the ketene dimer is selected from the group consisting of octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, β-naphthyl, and cyclohexyl-buttene dimers. Suitable ketene dimers are presented in U.S. Patent No. 4,279,794 and U.S. Patents Nos. 903,416; 1,373,788 and 1,533,434, and in the European Patent Application Publication No. 0,666,368 A3, which corresponds to the North American patent application Joint Stock No. 08 / 192,570 filed on February 7, 1994 (authorized), all of which are hereby incorporated by reference in their entirety. The ketene multimers for use in the process of this invention are disclosed in the co-pending US Patent Application Serial No. 08/601, 113, filed on February 2, 1996, which is incorporated herein in its entirety. It has a formula I wherein n is an integer of at least 1, R and R ", which may be the same or different, are a straight or branched chain alkyl group, saturated or unsaturated, having from 6 to 24 atoms of carbon, preferably from 10 to 20 carbon atoms, and more preferably from 14 to 16 carbon atoms; and R 'is a straight or branched chain saturated or unsaturated alkyl group having from 20 to 40 carbon atoms, preferably from 4 to 8 or from 28 to 40 atoms. The ketene multimers are also described in EP 0,629,741 Al, incorporated herein in its entirety, and in EP 0,666,368 A3, which corresponds to the North American Patent Application Serial No. 08 / 192,570, filed on February 7 of 1994. Particularly preferred groups of ketene dimers and ketene multimers for use in this invention are liquid ketene dimers and multimers which are preferably not solid at a temperature of 25 ° C (not substantially crystalline, semi-stannous or waxy solids; that is, they flow when heated without reaching the heat of fusion. More preferably, they are not in a solid state at a temperature of 20 ° C. With even greater preference, they are in a liquid state at a temperature of 25 ° C, and more preferably they are in a liquid state at a temperature of 20 ° C. These liquid dimers and multimers are typically mixtures of compounds of the formula I wherein n is preferably 0 to 6, more preferably 0 to 3, and especially 0; R and R ", which may be the same or different, are straight or branched chain alkyl groups, saturated or unsaturated, having from 6 to 24 carbon atoms, R 'is a straight or branched chain alkyl group, saturated or unsaturated , having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, and where at least 25% of the R and R "groups in the mixture of compounds is unsaturated. The liquid dimethyl ketene dimers and monomers may comprise a mixture of ketene dimer or multimer compounds which are the product of the reaction of a reaction mixture comprising unsaturated monocarboxylic fatty acids. The reaction mixture may also comprise saturated monocarboxylic fatty acids and dicarboxylic acids. Preferably, the reaction mixture for the preparation of the mixture of dimeric compounds or multimeric comprises at least 25% by weight of unsaturated monocarboxylic fatty acids, and more preferably at least 70% by weight of unsaturated monocarboxylic fatty acids. The unsaturated monocarboxylic fatty acids included in the reaction mixture preferably have from 10 to 26 carbon atoms, more preferably from 14 to 22 carbon atoms, and especially from 16 to 18 carbon atoms. These acids include, for example, oleic acid, linoleic acid, dodecenoic acid, tetradecenoic acid (myristoleic acid), hexadecenoic acid (palmitoleic acid), octadecadienoic acid (linolelaidic), octadecatrienoic acid (linolenic), eicosenoic acid (gadoleic), eicosatetraenoic acid (arachidonic) ), cis-13-docosenoic acid (erucic), trans-13-docosenoic acid (brasidic), and docosapentaenoic acid (clupanodonic), and their acid halides, preferably chlorides. One or more of the monocarboxylic acids can be used. Preferred unsaturated monocarboxylic fatty acids are oleic, linoleic, linolenic and palmitoleic acids, and their acid halides. Preferred unsaturated monocarboxylic fatty acids are oleic and linoleic acids, and their acid halides. The saturated monocarboxylic fatty acids used to prepare the dimeric and multimeric ketene compounds in this invention preferably have from 10 to 26 carbon atoms. carbon, more preferably from 14 to 22 carbon atoms, and especially from 16 to 18 carbon atoms. These acids include, for example, stearic, isostearic, myristic, palmitic, margaric, pentadecanoic, decanoic, undecanoic, dodecanoic, tridecanoic, nonadecanoic, arachidic and behenic acids, as well as their halides, preferably chlorides. One or more of the saturated monocarboxylic fatty acids can be used. Preferred acids are palmitic acid and stearic acid. The alkyldicarboxylic acids used to prepare the multimeric ketene compounds for use in this invention preferably have from 6 to 44 carbon atoms, and more preferably 9-10, 22 or 36 carbon atoms. Such dicarboxylic acids include, for example, cebasic, azelaic, 1, 10-dodecanedioic, suberic, brazilic, docosandioic acids, as well as C36 dimer acids, for example, EMPOL 1008 available from Henkel-Emery, Cincinnati, Ohio, USA. United States of America, and its halides, preferably chlorides. One or more of these dicarboxylic acids can be used. Dicarboxylic acids with 9-10 carbon atoms are especially preferred. The most preferred dicarboxylic acids are sebacic acid and azelaic acid. When dicarboxylic acids are employed in the preparation of the ketene multimers for use in this invention, the The amount of monocarboxylic acid (the sum of both saturated and unsaturated) is preferably about 5. A most preferred maximum is about 4, and the especially preferred maximum is about 2. The The mixture of dimeric and multimeric compounds can be prepared using known methods for the preparation of standard ketene dimers. In the first step, acid halides, preferably acid chlorides, are formed from a mixture of fatty acids, or a mixture of fatty acids and dicarboxylic acid, using PC13 or another halogenating agent, preferably chlorination. The acid halides are then converted to ketenes in the presence of tertiary amines (including trialkylamines and cyclic alkylamines), preferably triethylamine. The ketene portions are then dimerized to form the desired compounds. Suitable liquid ketene dimers and multimers for use in this invention are disclosed in US Patent Application Serial No. 08 / 428,288, filed on April 25, 1995, which is hereby incorporated by reference in its entirety, in the US Patent Application Serial No. 08 / 192,570, filed on February 7, 1994, and in US Patent Application Serial No. 08 / 601,113, filed on February 16, 1996. Alkyletone dimers are found available in the SSgAS ^ Kfe trade, as Aguapel® sizing agents, and in the form of dispersion as Hercon® emulsion sizes in Hercules Incorporated, Wilmington, Delaware. Non-solid ketene dimers at a temperature of 25 ° C can be achieved as Precis® sizing agents, also from Hercules Incorporated. Cellulose reagents are alkenyl succinic anhydrides (ASA). ASAs are components of unsaturated hydrocarbon chains that contain anhydride pendant groups succinic. They are usually made in a two-step procedure starting with alpha-olefma. The olefin is first isomerized by means of the random movement of the double bond from the alpha position. In the second step, the isomerized olefin reacts with maleic anhydride to provide the final ASA structure 2. Typical olefins employed for the reaction with maleic anhydride include alkenyl, cycloalkenyl and aralkenyl compounds containing from 8 to about 22 carbon atoms. Specific examples are isooctadedecylsuccinic anhydride, N-octadecenylsuccinic anhydride, n-hexadecenylsuccinic anhydride, n-dodecyl succinic anhydride, i-dodecenylsuccinic anhydride, n-decenylsuccinic anhydride, and n-octenylsuccinic anhydride. In the North American Patent No. 4, -040,900, which is incorporated here by reference in its entirety, and in The Sizing of Paper, second edition (paper sizing) edited by W.F. Reynolds, Tappi Press, 1989, by CE. Farley and R.B. Wasser, pages 51-62, alkenyl succinic anhydrides are disclosed. Various alkenyl succinic anhydrides that are commercially available from Albemarle Corporation, Baton Rogue, Louisiana. The amount of cellulose reactive size is preferably an amount sufficient to provide a sizing effect to the composition. At the lower end, the amount of cellulose reactive sizing in the composition is preferably greater than about 1% by weight of the weight of the aqueous composition, more preferably greater than about 5% by weight, and preferably even higher, higher that approximately 7% by weight. At the upper end, the amount of cellulose reactive size is preferably less than about 50% by weight of the weight of the aqueous composition, more preferably less than 30% by weight, and even more preferably less than 15% by weight. weight. The amount of cellulose reactive sizing in the composition is preferably from about 1 to about 50% by weight of the weight of the aqueous composition, more preferably from about 5 to about 30% by weight, and preferably even greater than about 7. to about 15% by weight. It has been found that it was difficult to predict in advance what Anionic polymers and combinations of cationic ingredients are effective in the present invention, except that this determination requires empirical methods. However, following the approaches presented herein, excessive experimentation by an expert in the art is not required to identify specific combinations of anionic water soluble polymers with polyvalent cationic additives that produce the desired rheological effect for a given application. In order to more clearly describe the present invention, the following non-limiting examples are offered. EXAMPLES To demonstrate the characteristics and usefulness of the present invention, several tests were employed in the examples, including tests to measure gravimetric water retention, Hercules sizing test, and Gurley porosity. The procedures for these tests are presented below. Gravimetric Water Retention (GWR): Water retention is measured using a Gravimetric Water Analysis Tester (Kaltec Inc., Novi, Michigan). Unless otherwise indicated, the test is carried out at atmospheric pressure (a setting of "0") for a period of 30 seconds. In this test method, 10 grams of solution are added to a circular cylinder that has a ~ - "" "- imOTninti ^ m cross section of 6.45 cm2 (1 square inch) and, in contact with a porous polycarbonate membrane (part No. GWR420, Kaltec Inc.). The membrane covers an absorbent pad (absorbent paper for GWR test, Kaltec Inc.). The absorbent pad is weighed before placing the solution in the cup, and then again after 30 seconds of contact time between the solution and the polycarbonate membrane. The amount of water weight gain of the absorbent pad is an indication of the water permeation of the solution through the membrane. A lower water weight gain of the absorbent pad indicates a higher water holding capacity of the solution. The gravimetric water retention value obtained by this method is provided in units of gms / m2, where lower values of GWR are preferred indicating greater water retention. Note that, in contrast to the yield point resistance, water retention is not an intrinsic property of a composition but rather describes the interaction of a composition with other materials. The water retention value, therefore, is affected by nature, for example, chemical composition, thickness and porosity, of the membrane used to make the measurement. Hercules Sizing Test (HST): In the Hercules Stencil Test (HST), a sheet of paper aa ¿HWh ^ ÜMMkMttttlfib it is placed under an ink solution containing 1% formic acid and 1.2% Naphthol Green B. The reflectance of the paper on the opposite side of the solution is initially measured and monitored as it falls due to ink penetration. The HST time (in seconds) is the time required for the reflectance to drop to 80% of its initial value. Higher HST values indicate higher levels of sizing. Gurley Porosity: Gurley's porosity measures the amount of time it takes for a known volume of air to flow through a sample. It is measured in seconds, and higher Gurley porosity values indicate a smaller sample porosity. Gurley's porosity is measured using a Model 1 Air Permeability Tester (Hagerty Technologies, Inc., Queensbury, NY) operated in accordance with the manufacturer's specifications. The tester is adjusted in the high pressure regulation, and the results offered are averages of five experiments. EXAMPLE 1 Solutions of various anionic water soluble polymers are prepared in water in concentrations sufficient to produce stock solutions having Brookfield viscosities greater than 500 cps. These mother solutions are then adjusted in concentration through the addition of water - ^ _- '--- MHM'? "'- complementary, and are agitated to provide solutions having Brookfield viscosities of approximately 100, 200, and 300 cps. The prepared solutions are tested for gravimetric water retention according to what is described above. For comparison purposes, the same solutions of anionic water soluble polymers described above or modified by the addition of each of several cationically charged additives as viscosity promoters. In most of these cases, a significant increase in the Brookfield viscosity of the solution is observed after mixing the solution with this cationic species. Each solution of water-soluble polymer that is modified with cationic additive is then diluted with addition of complementary water to produce solutions with viscosities of approximately 100 eos, 200 cps, and 300 cps. The solutions prepared in this way are then tested to determine the gravimetric water retention in the same way as the control solutions. The standard solution water retention test results appear next to the results for the cationically modified solutions in the following tables. In Table 1A, the first ionic polymer is sodium carboxymethylcellulose (CMC-9M31; Hercules Incorporated, Wilmington, DE) and the viscosity promoter is sodium acetate. basic aluminum (NIAPROOF; obtained from Union Carbide, New York, NY). TABLE 1A SODIUM CARBOXIMETHYLCULFOSE First Ionic Viscosity Retarder Viscosity Polymer CMC-9M31 Brookfield viscosity of gravimetric water by weight NIAPROOF solution, cps trica% by weight grams / m2 2% 1450 cps 1.25% 310 805 1. 11% 218 932 0. 86% 110 > 100 scale 1. 95% 0.039% 39, 000 0.64% 0.0129% 300 288 0. 53% 0.0105% 210 403 0. 39% 0.0078% 109 > 1000 In Table IB, the first ionic polymer is sodium carboxymethylhydroxyethylcellulose (CMHEC 420H; Hercules Incorporated, Wilmington, DE) and the viscosity promoter is a cationic polyDADMAC (RETEN 203; Hercules Incorporated, Wilmington, DE). CARBOXIMETHYL HYDROXIETILCELLULOSE IB BOARD First Viscosity Promoter of Ionic Retention CMHEC 420H Brookfield viscosity of gravity water «A, -» < a ^. > »^ J *» - '^ ttte by weight Retention 203 solution, metric cps% by weight grams / m * 1% 1,920 (cps 0.54% 290 970 0. 49% 205 > 1000 0. 37% 110 > 1000 0. 98% 0.117% 11.250 0.21% 0.025% 296 27 0. 19% 0.023% 210 22 0. 11% 0.013% 105 120 In Table IC, the first ionic polymer is anionic (non-standardized) pectin (LM103 AS-Z, Hercules Incorporated, Wilmington, DE) and the viscosity promoter is calcium chloride. IEC PECTIN TABLE First polymer Viscosity promoter of ionic retention Pectin Brookfield viscosity of water gravime- LM104 AS-Z Solution chloride, cps trica (not standardized) calcium grams / m Hercules% by weight% by weight 4% 688 3.13% 320 135 2.66% 200 335 2. 16% 108 751 3.75% 0.063% 27, 750 1.82% 0.031% 317 60 1.70% 0.029% 211 191 1.25% 0.021% 102 > 1000 In Table ID, the first ionic polymer is an anionic carrageenan (CARRAGEENAN J, Hercules Incorporated, Wilmington, DE) and the viscosity promoter is basic aluminum acetate (NIAPROOF, obtained from Union Carbide, New York, NY) or a dilute cationic polyDADMAC (RETEN 203; Hercules Incorporated, Wilmington, DE), as indicated. CARRAGENAN IDENTIFICATION TABLE First polymer Ionic Retention Viscosity Promoter Carrageenan Brookfield viscosity of gravi- ated water by weight wt.% Solution, metric cps grams / n 1% 1,836 0.52% 300 980 0. 45% 208 > 1000 0. 38% 104 > 1000 0. NIAPROOF / 0.039% 6,730 0.53% NIAPROOF / 0.021% 320 59 0. 39% NIAPROOF / 0.016% 185 55 0. 32% NIAPROOF / 0.013% 86 81 0. 98% RETEN 203 / 0.12% 17,900 0.12% RETEN 203 / 0.05% 288 out of scale In table IE, the first ionic polymer is an anionic carboxymethyl gum with a D.S. 0.5, and the viscosity promoter is basic aluminum acetate (NIAPROOF; obtained in Umon Carbide, New York, NY) or a dilute cationic polyDADMAC (RETEN 203; Hercules Incorporated, Wilmington). 1% 432 0.88% 308 922 0. 74% 216 > 1000 0.59% 113 > 1000 0. 98% NIAPROOF / 0.0392% 726 0.74% NIAPROOF / 0.029% 320 875 0.68% NIAPROOF / 0.027% 200 945 0.56% NIAPROOF / 0.022% 120 > 1000 0.98% RETEN 203 / 0.118% i, 916 - - - - ^.? Íí? ^ A ^ .., .--- .- - ~ ¡ü | -mm m-? Mtt ái ám 0. 21% RETEN 203 / 0.020% 296 > 1000 0.17% RETEN 203 / 0.019% 204 796 0.13% RETEN 203 / 0.016% 104 > 1000 In Table 1F, the first ionic polymer is a latex soluble in alkaline agents (ALCOGUM L-29, Aleo Products, Chattanooga, Tennessee), and the viscosity promoter is basic aluminum acetate (NIAPROOF; obtained from Union Carbide, New York). , NY). TABLE 1F LATEX SOLUBLE IN ALKALINE AGENT First polymer Ionic Retention Viscosity Promoter ALCOGUM Brookfield viscosity water gravime- L-29% by weight NIAPROOF of trica solution% in weight cps grams / m ' % 308 77 4. 16% 214 175 2. 38% 109 256 4. 88% 0.039% 382 4.07% 0.032% 276 37 3. 36% 0.027% 211 78 2. 03% 0.016% 113 151 In Table 1G, the first ionic polymer is a sodium alginate (KELGIN MV; Kelco, San Diego), and the viscosity promoter is calcium chloride. TABLE 1G r-daB-- * ~ fy-r? '- | il SODIUM ALGINATE First polymer Ion Retention Viscosity Developer Kelgin MV Brookfield viscosity of water % by weight Calcium Chloride solution, cps gravimetric weight in grams / m2 2% 3,016 1.05% 304 17 0. 88% 187 22 0. 68% 115 42 1. 88% 0.062% 44, 900 0.72% 0.024% 273 14 0. 57% 0.019% 203 15 0. 46% 0.015% 119 15 In table ÍH, the first ionic polymer is an anionic polyacrylamide (RETEN 215, Hercules Incorporated, Wilmington, DE), and the viscosity promoter is basic aluminum acetate (NIAPROOF; OBTAINED in Union Carbide, New York, NY). TABLE ÍH ANIONIC POLYACRYLAMIDE First ion polymer RETEN Viscosity Promoter 215 Brookfield Viscosity % by weight NIAPROOF solution, cps% by weight * "**" - - '- 0. 5% 730 0. 15% 288 0. 14% 215 0. 07% 113 0.44% 0.032% 3,028 0. 20% 0.015% 290 0. 15% 0.011% 224 0. 098% 0.007% 127 First ionic polymer Water retention RETEN 215 Gravimetric Percentage by weight grams / m2 0.5% 0.15% 137 0.14% 158 0.07% 643 0.44% 0.20% 11 0.15% 14 0.098% 52 COMPARATIVE EXAMPLE 1: Interactive complexes of soluble polymers in water such as, for example, polyacrylamide ammonium copolymers and xanthan gum, with cationic additives, similar to the experiments shown in Tables 1A-H above. Attempts are also made to prepare interactive mixtures of cationic and anionic guar as shown in Table II. However, in all these cases, no rheological benefits were observed in mixtures of these particular water-soluble polymers and cationic additives. The fact that the anionic polyacrylamide does not provide the rheological benefit of improved water retention when mixed with cationic additives may be the result of this tendency of the polymer to be strongly precipitated when mixed with cationic species as illustrated in tables 1J and 1K . This finding shows that the prior art description of mixtures of anionic and cationic polyacrylamide copolymers useful for making paper must involve a totally different mechanism from that of the present invention. The comments regarding the use of the anionic and cationic mixtures of the prior art clearly do not lead to the present invention based on these findings. In addition, the inability to prepare mixtures of either cationic or anionic polyacrylamide copolymers with oppositely charged additives that were useful for the property of increased water retention (tables 1J, 1K, and ÍM), or to prepare mixtures of cationic guar with anionic guar useful for the improved water retention property (table ÍL) leads to the conclusion that the present > afe ..... ¿¿, ", invention of effective combinations of positively charged ingredients to provide an improved property of water retention is not evident from the prior art uses of these particular polymers. TABLE II XANTANO RUBBER Polymer soluble in,% by weight cps 1% 1,144 0.29% 336 0.17% 188 0.98% RETEN 203 / 0.117% 2,176 0.23% RETEN 203 / 0.027% 312 0.19% RETEN 203 / 0.022% 220 0.98% NIAPROOF / 0.039% 8,045 0.32% NIAPROOF / 0.012 % 315 0.24% NIAPROOF / 0.009% 213 Water soluble polymer Retention of KELTROL RD (Kelco Inc.) water Xanthan gum Gravimetpca Percentage by weight grams / m2 1% 0.29% 962 0. 17% > 1000 0.98% 0.23% > 1000 0.19% > 1000 0.98% 0.32% > 1000 0.24% out of scale TABLE 1J ANION POLYACRILAMIDE Water soluble polymer * by weight Viscosity of RETEN 235 (Brookfield additive Hercules of Incorporated) cation co solution, cps Ammonium polyacrylamide% by weight 0.5% 2,382 0.28% 310 0.19% 215 0.098% 117 0.5% 0.0083% Retain 203 strong precipitate 4,475 0.147% 0.0024% Retain 203 320 0.096% 0.0016% Retain 203 225 0.049% 0.0008% Retain 203 122 0.5% 0.01% Galactosol strong precipitate 813S guar gum Cationic Hercules Water soluble polymer Retention of RETEN 235 (Hercules water Incorporated) Gravimetric Anionic polyacrylamide grams / m2 Weight percentage 0.5% 0.28% 27 0.19% 31 0.098% 53 0.5% 0.147% 31.3 0.096% 54 0.049% 250 0.5% TABLE 1K ANIONIC POLYACRYLAMIDE Water soluble polymer Viscosity additive RETEN 215 (cationic Brookfield Hercules of Incorporated) Retention 203 solution, cps Anionic polyacrylamide% by weight% by weight 0.5% 730 0.15% 288 0.14% 215 ¡ÉSih ¡Ju * ÍÍÍÍÍÍÍiá M3Ím¡tt. 0. 07% 113 0.5% 0.0076% 730 (strong precipitate) 0. 21% 0.0030% 284 0.15% 0.0022% 195 0.09% 0.0014% 120 Water-soluble polymer Retention of RETEN 215 (Hercul is water Incorporated) Gravimetpca Polyacrylamide ammonia grams / m2 0.5% 0.15% 137 0.14% 158 0.07% 643 0.5% 0.21% 306 0.15% 589 0.09% 732 TABLE I MIX ANTIQUE GUAR MIX AND GUAR CATIÓNICA Guar ammonium Guar catiomca Carboxylmethyl gum viscosity GALACTOSOL 813S Brookfield (DS 0.5) (Hercules mcorporated)% wt% wt. Solution, cps 1% 353 . ^ JMM- ».. ^ ... ^ Mfc ^ ll 1,707 0.5% 0.5% 49 0.34% 0.66% 146 TABLE IM 5 CATIÓN POLYACRILAMIDE COPOLYMER Water soluble polymer Anionic additive Viscosity of PERCOL 745 (Allied CMHEC-420 Brookfield Colloids) Carboxymethyl polyacrylamide hydroxyethylcellulose copolymer solution, Cationic% by weight cps% by weight 0.5% 345 cps 0.5% 0.01% strong precipitate EXAMPLE 2 15 Solutions selected from example 1 are measured to determine the resistance to yield point values with very low cutting speed using a Bohlin rheometer. The solutions include a control solution of non-ionic xanthan gum and solutions of CMHEC 420, with and without cationic additives present. All tested solutions are prepared at constant Brookfield viscosity levels by diluting stock solutions until viscosities of approximately 300 cps are obtained. These tests are found that the values of resistance to yielding point of the anionic soluble polymer solution with , A ». ^^.» M ^ - Ja ^ _, ^ .-. ^ ... ^^? ^^^ L? ^ JMBlß? T. m ._- ^? áfñar ..- ^ AaaM Present cationic additive, at a given Brookfield viscosity, are significantly higher than the anionic polymer alone or the xanthan control solution. These results appear in table 2. These findings are significant to indicate potential utilitarian properties since xanthan gum, a non-ionic polymer, is currently used in many industrial applications due to its high resistance to yield point, which is well established in technical literature. It is therefore evident that aqueous solutions of any newly discovered water-soluble polymer mixture, which exhibits yield point strength values of greater magnitude than the yield point resistance values of xanthan gum at a low viscosity, is an unexpected discovery. Thus, the present invention includes low viscosity solutions of water soluble polymers in combination with cationic additives, which show yield strength values greater than about 30 dynes / cm 2. TABLE 2 COMPARISON OF RESISTANCE TO POINT OF GRANTS OF XANTANO RUBBER COMPARED WITH ANIONIC / CATIÓNICOS DE POLÍMEROS SOLUBLES EN AGUA FIRST% wt. Strength Viscosity Resistance Promoter Brookfield viscosity polymer of ionic point Reten 203 solution, transfer agent by weight cps dyne / cm2 Rubber of 0.29% 336 12.5 Xantane Keltrol RD (non-ionic, control) Carboxymethyl 0.57% 290 10.1 Sodium cellulose CMHEC-42OH Carboxymethyl 0.21% 0.025% 296 39.8 Sodium Cellulose CMHEC-42OH EXAMPLE 2B In this example, it is demonstrated that complexes of anionic water-soluble polymers with cationic complexing agents produce yield point values at a given Brookfield viscosity that significantly exceed the resistance values. to transfer point of natural gums. The finding of means to produce these remarkable yield strength values in low viscosity solutions is itself an unexpected discovery, and the fact that the utility of this property has been identified, even though it was not previously recognized in the prior art, it also represents an unexpected discovery. In each of tables 2B and 2C, the components are added sequentially in descending rows. Solutions of xanthan gum in water are prepared by adding 15 parts by weight of the gum to 985 parts by weight of water, and stirring to dissolve for 2 hours to prepare a stock solution. Aliquots of the stock solution are adjusted in concentration by addition of additional water, as shown in Table 2B, to produce Brookfield viscosities, either about 1000 cps (RVT # 2/12 RPM) or about 500 cps. Solutions of sodium alginate in water are prepared by the addition of 20 parts by weight of Scogin® MV sodium alginate to 980 parts by weight of distilled water, and by stirring to dissolve for two hours to prepare a stock solution. Aliquots of the stock solution are adjusted in concentration, by the addition of additional water, as shown in Table 2B, to produce Brookfield viscosities either at about 1000 cps (# 2/12 RPM) or about 500 cps. A stock solution of CMC-7H3SC which forms complexes with aluminum sulfate in water is prepared by the addition of 10 parts by weight of CMC-7H3SC to 990 parts by weight of distilled water, stirring until dissolved for 2 hours, and adding 30 parts in, fieso. of magnesium sulfate, followed by 20 parts by weight of 2% aluminum sulfate hydroxide. It is observed that it forms a weak gel. Aliquots of the stock solution are adjusted in concentration by addition of water as shown in Table 2B, to produce Brookfield viscosities of approximately 1000 cps (LVT # 2/12 RPM) or approximately 500 cps. Solutions of three rheological modifiers in aqueous starch solution were prepared by first firing and dissolving a 10% solution of Penford 280 ethylated starch in distilled water, and then dissolving in this the various gums of ingredients illustrated in Table 2C. The Brookfield viscosity of these solutions are then adjusted to achieve target values of approximately 500 cps and 1000 cps by the addition of additional aliquots of 10% Penford 280 starch solution, which had the effect of adjusting the concentrations of the gums at a level that could produce the desired viscosities. Measurements of resistance to transfer point for the polymer solutions mentioned above are carried out using an AR1000 rheometer (Ta Instruments) with standard methodology. TABLE 2B Components 1 2 3 4 5 6 (parts by weight) Initial water 980 985 990 980 985 990 CMC-7H3SC 10 10 Xanthan gum 15 15 Keltrol® RD Sodium alginate 20 20 Scogin MV Epsom salt 30 30 added 2% alum 20 20 added water added 333 3000 213 652 4769 261 RESULTS Viscosity of 1000 1010 1070 480 515 530 Brookfield to cps cps cps cps cps cps ° C LVT # 2/12 RPM Resistance to 3.25 12.5 13.7 0.7 6.09 8.9 Transfer point (Dina / cm2) TABLE 2C Components 1 2 3 4 5 6 (parts by weight) solution 100 100 100 100 100 100 Penford starch 280 at 25 ° C at 10% Cationic resin 1.2 0.9 Kymene 557H @ % active Xanthan gum 1 1 Keltrol RD Sodium alginate 1.5 1.5 Scogin MV CMC-7H3SC 1.5 1.5 solution Starch Penford 280 at 10% at 65 ° C RESULTS Viscosity of 1082 960 1025 550 515 475 Brookfield to cps cps cps cps cps cps 65 ° C LVT # 2/12 RPM Resistance to 12.33 0.76 54.96 5.88 0.28 16.98 Discharging point (Dina / cm2) As shown in table 2B, in the aqueous solution without starch, it is found that the values of yield point resistance of the CMC / aluminum solution complexes are higher than the yield point resistance values of xanthan gum and sodium alginate solutions at the same Brookfield viscosities. As shown in Table 2C, in the starch solutions containing the various gums and gum complexes it was found that the yield point resistance of the complex CMC / Kymene 557H was significantly higher than the resistance to the transfer point of controls of sodium alginate and xanthan gum. EXAMPLE 3 Aqueous solutions of carboxymethylhydroxyethylcellulose CMHEC 420H are prepared with cationic modifier, and various sizing agents are added as additives to these solutions. The complementary additives are styrene-maleic anhydrides (Scripset 740 and 742, Hercules Incorporated), a chetane multimeric sizing agent made from 2 moles of sebacic acid and 1 mole of unsaturated fatty acids (PTD D-898, Hercules Incorporated), an alkyl mercane dimer made from linoleic and oleic acids (PRECIS; Hercules Incorporated) and a latex colloid sizing agent (Chro aset 600, Hercules Incorporated). It is found that the mixtures of polymers soluble in anionic water and cationic modifier form compatible solutions with each of their additives, with the exception of the alkenyl succinic anhydride. It is stated that the technology of the present invention can be operated for use in surface sizing applications in combination with sizing agents and colloids. These results appear in tables 3A and 3B. TABLE 3A MIXTURE OF A FIRST ANIONIC IONIC POLYMER AND PROMOTER OF CATIÓN VISCOSITY WITH APPRENTICE AGENTS Components: 1 2 3 4 5 6 solution CMHEC-420G 400 400 400 400 400 400 at 0.25%, grams Dilute Reten 203, 10 10 10 10 10 10 (6% active), grams Scripset 740 40 (Hercules), grams Scripset 742 40 (Hercules), grams AQU D-898 (Hercules) 40 sizing agent Chromaset 600 40 (Hercules) sizing agent Precis (Hercules) 40 agent sizing Alkenyl succinic anhydride 40 Brookfield solution 24 11 4 23 5 ppt solution, cps Water Retention 134 270 > 1000 14 > 1000 gravimetric grams / m2 TABLE 3B MIXES OF A FIRST ANIONIC IONIC POLYMER AND CATICONIC PROMOTER OF VISCOSITY WITH BENTONITE CLAY First ion polymer VOLCLAY HPM-75 Promoter of CMHEC-42OH BENTONITA viscosity% by weight (Am. Colloid) RETEN 203% by weight% by weight 0.98 1.96% 0.49 0.98% 0.43 0.86% 0.20 0.41% 0.96 1.92% 0.12% 0.25 0.49% 0.030% 0.20 0.38% 0.024% First ion polymer CMHEC-2OH Retention Viscosity Brookfield water% by weight of gravimetca solution, grams / cm2 cps 0.98 2.928 0.49 285 868 0.43 205 957 0.20 111 > 1000 0.96 10.200 0.25 185 40 0.20 100 64 «» < A > > EXAMPLE 4 An aqueous solution of hydroxyethylated starch of 10% Penford 280 gum (Penford products, Iowa) is prepared by baking the gum in water for one hour at a temperature of 95 ° C with 0.20% by weight of carboxymethylhydroxyethylcellulose CMHEC- 420H (Hercules Incorporated, Wilmington, DE). The starch solution is weighed and then cooled to a temperature of 70 ° C, and divided into aliquots. A sizing agent is added to the thickened starch solution, and then a cationic Reten 203 polymer diluted in aliquots in the starch solution is added. This solution, in different stages of cationic additive level, is measured to determine Brookfield viscosity and gravimetric water retention. It is observed in these tests that the improvement of water retention performance rises as more cationic additive is added. These results appear in Table 4. This example shows the potential for the production of improved sizing results by using the present invention with starch and sizing agents for the surface treatment of paper. TABLE 4 USE OF A FIRST ANIONIC AND PROMOTOR IONIC POLYMER CATIÓNICO DE VISCOSIDAD WITH STARCH AND AGENT OF APRESTO DISSOLVED Components: 1 2 3 4 5 Solution of CMHEC-420H 450 450 450 450 450 AL 0.20% / starch Penford 280 10% Sodium bicarbonate 0.2 0.2 0.2 0.2 0.2 grams Scripset 740 50 50 50 50 50 (Hercules) grams Dilute Reten 203, 2 4 6 8 10 (6% active), grams Viscosity of 55 68 85 110 148 Brookfield of Solution at 70 ° C, cps Water Retention > 1000 690 163 36 35 gravimetric grams / m2 EXAMPLE 5 Compositions of an ionic polymer (sodium carboxymethylcellulose), a viscosity promoter (KYMENE 557H), and a moderation agent (hydroxyethylated starch) are prepared in the following manner. An aqueous solution of 8% hydroxyethylated starch (PENFORD GUM 280) is prepared by cooking the gum in water for one hour at a temperature of 95 ° C with 0.25% by weight of sodium carboxymethylcellulose (CMC-7H3SX; Hercules Incorporated, Wilmington, DE). The heavy starch solution is then cooled to a temperature of 70 ° C and divided. Various levels of Kymene 557H (Hercules Incorporated, Wilmington, DE) are added to aliquots of the starch solution, and compared to determine Brookfield viscosity and gravimetric water retention. It is observed that the addition of Kymene 557H increases both the viscosity and the water retention of the solution relative to the control test without Kymene 557H. These results appear in table 5A. In the parallel table, compositions without the moderation agent are prepared. A 1% solution of CMC-7H3SX is prepared, then the solution is measured to determine the Brookfield viscosity. A small amount of Kymene 557H cationic polymer is added to the CMC solution with stirring. In this comparison example, however, a precipitate is observed, and the viscosity of the solution decreases as more Kymene 557H is added. This indicates a depletion of the CMC polymer from the aqueous phase. This is shown in table 5B. This example shows that the presence of dissolved starch as a moderation agent allowed the use of a CMC composition and a cationic modifier to achieve the property of improved water retention useful solution, while the absence of the dissolved starch moderation agent caused precipitation, and is not effective for the use of Kymene with CMC for improved water retention.

TABLE 5A CMC AND COTTON MODIFIED WITH VISCOSITY PROMOTER Moderation Agent First polymer Viscosity promoter PENFORD 280 Ionic solution CMC-7H3S KYMENE 557H Ethyl starch% by weight% by weight 8% 0.25% 0.025% 8% 0.25% 0.050% 8% 0.25% 0.075% 8% 0.25% Moderation Agent Viscosity promoter Water retention PENFORD 280 Brookfie solution: gravimetric ld of ethylated starch (at 70 ° C) grams / m2 8% 190 cps 35 8% 230 cps 33 8% 255 cps 31 8% 170 cps 170 TABLE 5B SOLUTION MIX CMC WITH KIMENE 557H First ion polymer Viscosity promoter Viscosity of CMC-7H3SX KIMENE 577H Brookfield wt% wt% solution, cps 1% 1100 cps 4 0.99% 0.012% 700 cps, precipitated 0.! 0.024% 540 cps, precipitated EXAMPLE 6 An aqueous solution of 8% Penford Gum 280, hydroxyethylated starch is prepared by baking the gum in water at a temperature of 95 ° C. The starch solution cooked with 0.25% by weight of CMC-7H3S (Hercules). The heavy starch solution is then cooled to a temperature of 70 ° C and divided. Several levels of Kymene 557H are added to aliquots of the starch solution, and compared to determine the Brookfield viscosity and gravimetric water retention. The starch solutions obtained in this way are then used to surface-treat uncoated paper sheets using a rod pull method. The paper sheets treated in this way are dried at a constant temperature, and the humidity is then measured for absorption of dry starch and Gurley porosity with a Hagerty digital porosimeter (Hagerty Technologies Inc., Queensbury, New York). It is found in these tests that the combined CMC / Kymene 557H modifier produces much higher Gurley porosity values of the treated paper sheets than the control tests. This results they are shown in table 6. A higher Gurley po porosity is a desired property on paper treated with sizing press. This example demonstrates the utility of the present invention for providing valuable flow properties to starch solutions employed for the surface treatment of paper. TABLE 6 USE OF CMC AND STARCH IN COMBINATION WITH KYMENE® 557H FOR USE IN SURFACE TREATMENT OF PAPER SHEETS Viscosity Promoter Water Retention Viscosity KYMENE 557H Gravimetric Brookfield % by weight solution gram / m2 0.025% 190 cps 35 0.050% 230 cps 33 0.075% 255 cps 31 170 cps 170 Viscosity Promoter Porosity Absorption of KYMENE 557H starch on Gurley paper% by weight% by weight (treated paper) 0. 025% 1.7 314 0.050% 1.9 294 0.075% 1.0 605 2.1 254 EXAMPLE 7 A coating formulation of rotogravure paper is prepared by dispersing 200 grams of Hydraprint delaminated clay (JM Huber, Macon, Georgia) and 200 grams of Hydrasperse # 2 kaolin clay (JM Humber, Macon, Georgia) in 400 grams of water, then mixing this with 48 grams of a rotogravure latex RAP 3 B3NABK (50% active) (Dow Inc., Midland, Michigan). The mixture is then adjusted to a pH of about 8.5-9.0 with ammonia hydroxide to obtain a masterbatch. To a given amount of masterbatch, rheology modifiers of base formula are added to thicken the mixture. In the case of control, Polyphobe 205 is used, an associative thickener (Union Carbide, Danbury, Connecticut), which is known as a thickener used commercially for coatings of rotogravure paper, in order to thicken the coating. In the comparison test experiment, CMHEC-420H is dissolved in the base coat formula, and then a cationic polymer purifier, RETEN 203, is added to the system. The paper coating properties of the control and comparative test are measured after. It is found that the combination of CMHEC-420H with a cationic additive offers a significantly better water retention than the control test while providing a high cut value of Hercules low similar to the control case. These ayazos are found in Table 7 indicate the utility of the present invention for providing novel desirable properties to paper coatings. TABLE 7 COMPARISON OF THICKENING AGENTS FOR PAPER WRAPPING Water, grams 400 400 Disappointed clay, grams 200 200 Pigment # 2, grams 200 200 Retrogravure latex 48 48 (59%), grams Ammonia up to a pH of 8.5-9 Polyphobe 205, 5.4 (Union Carbide), CMHEC 420, stirring 0.8 grams until dissolution Brookfield Viscosity 408 cps 650 cps coating (RTV) Dilute Reten 203, ( 6% active) 13.6 grams Brookfield viscosity 610 cps RVT coating Water retention GWR 359 grams / m2 441 grams / m2 (pressure 2 atmospheres, duration: 60 seconds) . -jTafc * High cut viscosity 12 cps 12 cps Hercules, at a cutting speed of 46,000 sec-1, second pass EXAMPLE 8 A mixed solution of 10% by weight of hydroxyethylated starch Penford 280 and 0.2% of CMHEC-420H is prepared in water by adding these ingredients to the water with stirring and then subjecting the solution to cooking at an elevated temperature of 95 ° C for at least one hour. To 1000 parts by weight of this solution several agents are added and the effects of these additives on the viscosity and water retention of GWR are measured. In the cases of control, solutions of aluminum sulfate mixed with citric acid according to the prior art of US Patent No. 4, 035, 195 are added to the starch solution. These are presented in Table 1Y, columns 2 and 4. In a comparison experiment, a cationic polymer of the present invention is added to the starch / CMHEC-420H solution. It is shown in table 1Y, columns 1 and 3. Portions of these compositions are adjusted either to a pH of 6.5 (columns 1 and 2) or to a pH of 8.5 (columns 3 and 4), through an addition of a sufficient amount of ammonium hydroxide. As shown in table 1Y, it is found that the best Solution viscosity is significantly higher with the CMHEC / cationic additive of the present invention compared to CMHEC / alum / mixed citrate of the prior art. It was also found that, at a pH of 8.5, the water retention of the present invention was significantly higher than in the case of the prior control technique. It could therefore be shown that the addition of a mixed solution of ammonium sulfate / sodium citrate, as in US Patent No. 4,035,195, of the prior art is not operable in the present invention to improve the water retention of solution in the high pH condition which would be typical in many sizing press applications. TABLE 8A EFFECTS OF ALUMINUM SULFATE / SODIUM CITRATE ON CMHEC 1 2 3 4 (control) (control) Penford solution 280 1000 1000 1000 1000 10% / CMHHEC 420H 0.2%, parts by weight, Aluminum sulphate 9.4 9.4 3. 2% / citric acid 0.4%, parts by weight, Solids Retain 203, 4 4 parts by weight, pH * 6.5 6.5 6.5 6.5 Solution viscosity 131 97 418 65 Water retention GWR, 71 48 105 299 gm / m2 at 30 seconds * pH adjusted with ammonium hydroxide COMPARATIVE EXAMPLE 8B A 1% solution of CMC-7H3S is prepared in water and the viscosity is measured . To 1000 parts by weight of this solution, 26 parts by weight of Bacote 20 (Magnesium Electron), zirconium ammonium carbonate, are added with stirring. It is found that the viscosity of the solution decreases with the addition of Bacote 20. In separate experiments, this effect of decreasing viscosity is found in a high range of addition levels of ammonium zirconium carbonate. Both the CMC and the CMC / zirconium solutions are mixed with additional dilution water to produce solutions of approximately 300 cps of viscosity and the GWR retentions are measured. It is found that the two CMC solutions, both zirconium and zirconium free, have very similar water retention values. These results appear in table 8B. Accordingly, it is shown that the addition of a zirconium salt, as in U.S. Patent No. 5,362,573, does not serve in the present invention to improve the retention of water in solution. TABLE 8B fc £ -f- -? g EFFECTS OF ZIRCONIUM SALT ON THE PROPERTIES OF CMC SOLUTION 1 2 3 4 Solution CMC-7H3S at 1%, 1000 1000 1000 1000 parts Ammonium carbonate zircomo Bacote 20, parts Water dilution, parts 400 320 Solution viscosity Water retention GWR, 754 754 gm / m.2 at 30 seconds EXAMPLE 9 Paper having a basis weight of 99 g / m2 is prepared in a commercial paper making machine from a combination of wood pulp soft and hard wood. The paper has a 12% ash by weight and the filler employed is a precipitated silica of the HO type. Other typical papermaking additives are used, but the paper does not contain added internal sizing agents, and the paper is not treated in a sizing press. The paper is dried and stored in the form of rolls. The paper is then treated in a pilot film transfer sizing press equipped with a dipstick to control the level of additive solution. The rod adds the solution in a coating roller that then transfer the treatment to paper. The treated paper is passed through a dryer section and rewound on a reel. The paper is treated with starch and additives only on one side. During the coating process, the paper moves to 1066 meters (3,500 feet) linear / minute. The components of the rheology modification system and sizing agent are added separately to the starch solution. The cationic resin is added first, and the sizing agent is added to the end. The paper is coated with the sizing press solution within 6 minutes of the addition of the sizing agent. The rheology modification system increased the viscosity of the starch to approximately 80 cps. After aging after two weeks, samples are taken from the final reel for evaluation. In each case, the amount of starch added is 1.8 g dry / m.2 of the dry paper. The starch solution is employed at a pH of 8 at a temperature of 57 ° C, and has a Brookfield viscosity of about 20 cps with spindle 1 and 100 revolutions per minute. The rheology modification system comprises Kymene 577H and CMC-7H3SC, and is added to the paper in the amounts shown in Table 9. The paper is treated with a solution of 8% ethylated starch to which a) a system is added of rheology modification, b) a sizing agent or c) a combination of both.

The M1322 sizing system, an alkenylkene dimer arrangement, is a product of Hercules Incorporated. The dimer is in the liquid state at room temperature. Kymene 577H, a polyamide with cationic azetidium functionality, is manufactured and sold by Hercules Incorporated in the form of a wet strength additive for paper. CMC-7H3SC is a carboxymethylcellulose manufactured by Hercules Incorporated. The sample of CMC-7H3SC employed in this example has a substitution degree of 0.7 (ie, 70% of the methylhydroxy groups of the cellulose react to form the carboxy group). Samples are evaluated for sizing (water resistance) in accordance with one measured by the Hercules standard test (HTS). The results appear in table 9. TABLE 9 a bl cl b2 c2 Kymene 557H 0.014 0.014 0.014 (g / m2 of dry paper) CMC-7H3SC 0.039 - 0.039 0.039 (g / m2 dry paper) M1322 dimer - 0.036 0.036 0.040 0.040 (g / m2 dry paper) HST (sec.) 0 31 70 56 12 b3 c3 Kymene 557H 0.014 • '-' • - «- &AM- da. ~ * lih r? ¥ i? iiiMiin i i i (g / m2 of dry paper) CMC-7H3SC 0.039 (g / m2 of dry paper) M1322 dimer 0.054 0.054 (g / m2 of dry paper) HST (sec.) 102 137 The addition of the rheology modifier with the sizing agent increase the level of paper size according to HST that is obtained for each level of sizing agent. The rheology modifier alone does not increase the size of the paper under the conditions of the test. EXAMPLE 10 Under ordinary conditions, when a solution of carboxymethylcellulose (CMC) in water is mixed with a solution of a highly cationic polymer, for example Kymene 557H, formation of a precipitate is typically observed, with a concomitant decrease in viscosity. Such blends do not exhibit a significant thickening effect when added to a paper coating composition. This example illustrates that a mixture of an anionic polymer, a cationic polymer and a moderating agent is an effective thickener for paper coating composition. 10 parts of CMC-9L1EL are dissolved in 100 parts of water, then 5 parts of sodium citrate dissolve in the water, mt ^^^ í? followed by 48 parts Kymene 557H cationic resin. A clear solution is observed. The solution thickens markedly over the course of two days of storage, but does not form gel. A parallel experiment incorporating 80 parts of Kymene 557H as the final component forms a viscous clear solution after two days of storage. The CMC / Kymene solution formed above is added to a paper coating containing kaolin clay and calcium carbonate pigments and SBR latex with 64% solids. A ratio of 5 parts of CMC / Kymene solution complex is added to 100 parts by weight of the paper coating. It is noted that the Brookfield viscosity of the coating increases from 200 cps to 5,000 cps which indicates a very strong thickening effect, and the thickening coating in this way has a very smooth appearance without the formation of visible lumps or agglomerates. In a control experiment, a small amount of Kymene 557H is titrated in the same paper coating composition. In this case, a strong pigment agglomeration is observed consisting of hard lumps of varying size in the coating. Even though the invention has been described with reference to particular means, materials and modalities, it is understood that the invention is not limited to the specific details disclosed if not extending to all its equivalents within the scope of the claims.

Claims

CLAIMS An aqueous composition comprising at least a first ionic polymer and at least one viscosity promoter, said at least one viscosity promoter comprising at least one second ionic polymer having a net ionic charge opposite to the net ionic charge of said at least first ionic polymer, said aqueous composition has a resistance to yield point greater than about 5 dynes / cm2. The aqueous composition according to claim 1, wherein said aqueous composition has a resistance to yield point greater than about 10 dmas / c 2. The aqueous composition according to claim 2, wherein said aqueous composition has a higher yield point resistance that approximately 20 dynes / cm2. The aqueous composition according to claim 3, wherein said aqueous composition has a yield point strength greater than about 30 dmas / cm2. The aqueous composition according to claim 4, wherein said aqueous composition has a resistance to yield point greater than about 50 dynes / m2. 6. The aqueous composition according to claim 5, wherein said aqueous composition has a resistance to yield point greater than about 70 dmas / cm2. 7. the aqueous composition according to claim 1, wherein said aqueous composition has a Brookfield viscosity less than about 10,000 cps. The aqueous composition according to claim 7, wherein said aqueous solution has a Brookfield viscosity less than about 5,000 cps. 9. The aqueous composition according to claim 8, wherein said aqueous composition has a Brookfield viscosity less than about 1,000 cps. 10. The aqueous composition according to claim 9, wherein said aqueous composition has a yield point strength greater than about 10 dynes / cm2. 11. The aqueous composition according to claim 10, wherein said aqueous solution has a resistance to yield point greater than about 20 dynes / cm2. 12. The aqueous composition in accordance with "*- --to*""" -*:-***. Claim 11, wherein said aqueous composition has a yield point strength greater than about 30 dynes / cm2. The aqueous composition according to claim 9, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. The aqueous composition according to claim 13, wherein said aqueous composition has a yield point strength greater than about 10 dynes / cm 2. 15. The aqueous composition according to claim 14, wherein said composition has a yield point strength greater than about 20 dynes / cm2. 16. The aqueous composition according to claim 15, wherein said aqueous composition has a resistance to yield point greater than about 30 dynes / cm2. The aqueous composition according to claim 13, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. 18. The aqueous composition according to claim 17, wherein said aqueous composition has a resistance to yield point greater than approximately 10 dynes / cm2. 19. The aqueous composition according to claim 18, wherein said aqueous composition has a yield point strength greater than about 20 dynes / cm2. The aqueous composition according to claim 19, wherein said aqueous composition has a resistance to yield point greater than about 30 dynes / cm 2. 21. The aqueous composition according to claim 17, wherein said aqueous composition has a Brookfield viscosity greater than about 50 cps. 22. The aqueous composition according to claim 1, wherein said at least one first ionic polymer is a polymer having a net anionic charge and said at least one second ionic polymer is a polymer having a net cationic charge. 23. The aqueous composition according to claim 22, wherein said at least one first ionic polymer has a net anionic charge of at least about 0.04 meq / gram. 24. The aqueous composition in accordance with Claim 22, wherein said at least one first ionic polymer comprises at least one of the following: anionic polysaccharide, anionic polysaccharide derivative, and synthetic anionic polymer. 25. The aqueous composition according to claim 22, wherein said at least one first ionic polymer comprises at least one anionic polysaccharide which is carrageenan, pectin, or sodium alginate. 26. The aqueous composition according to claim 22 wherein said at least one first ionic polymer comprises at least one anionic polysaccharide derivative comprising carboxymethylcellulose, carboxymethylguar, carboxymethylhydroxypropylguar, carboxymethylhydroxyethylcellulose, methylcarboxymethylcellulose or carboxymethyl starch. 27. The aqueous composition according to claim 22 wherein said at least one first ionic polymer comprises at least one anionic polysaccharide derivative which is a carboxymethyl cellulose 28. The aqueous composition according to claim 22, wherein said at least one first ionic polymer comprises at least one derivative of .HidfaMBÜtt. . «Fa ----" - "•« - "- anionic polysaccharide which is a carboxymethylhydroxyethylcellulose. 29. The aqueous composition according to claim 22, wherein said at least one first ionic polymer comprises at least one synthetic anionic polymer which is a copolymer of anionic acrylamide, a copolymer of amphoteric acrylamide, or polyacrylic acid polymer or acid acrylic. 30. The aqueous composition according to claim 22 wherein a solution having 10% by weight or less of said at least one first ionic polymer in water has a Brookfield viscosity at room temperature greater than about 1,000 cps. 31. The aqueous composition according to claim 22 wherein said at least one first ionic polymer comprises at least one of the following: sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose; pectin; carrageenan; carboxymethyl guar gum; sodium alginate; anionic polyacrylamide copolymers; latex soluble in alkalis; carboxymethylcellulose; and carboxymethylhydroxypropylguar. 32. The aqueous composition according to claim 22 wherein said at least one first - »- *» --- - «- The ionic polymer is carisóxymethylhydroxyethylcellulose and said at least one viscosity promoter is a diallyldimethylammonium chloride polymer. The aqueous composition according to claim 22 wherein said at least one first ionic polymer is carboxymethylcellulose and said at least one viscosity promoter is a reaction product of epichlorohydrin of a polyaminoamide obtained by reaction of adipic acid with diethylenetriamma. The aqueous composition according to claim 22 wherein said at least one according to the ionic polymer comprises at least one cationic polyacrylamide; reaction product of epihaiohydrin of polyaminoamides obtained by reaction of polyamines with dicarboxylic acids; or diallyldimethylammonium chloride polymer. The aqueous composition according to claim 22 wherein said at least one second ionic polymer comprises at least one of the following: cationic polyacrylamide; reaction product of epihaiohydrin of polyaminoamides obtained by reaction of polyamines with dicarboxylic acids; diallyldimethylammonium chloride polymer, polyamide-epichlorohydrin resins, polymerization products ^^^^ | of quaternary monomers, copolymers of quaternary monomers with other reactive monomers, and adducts of quaternary epoxides with water-soluble polymers. 36. The aqueous composition according to claim 22 wherein said at least one viscosity promoter further includes at least one inorganic salt having a polyvalent functionality. 37. The aqueous composition according to claim 22 wherein said at least one viscosity promoter comprises at least one multivalent metal cation. 38. The aqueous composition according to claim 37 wherein said at least one viscosity promoter comprises a salt of at least one of the following: aluminum, magnesium, iron III, calcium, and zinc. 39. The aqueous composition according to claim 22 wherein a solution having 5% by weight of said at least one second ionic polymer in water has a Brookfield viscosity at room temperature less than about 2,000 cps. 40. The aqueous composition according to claim 39, wherein said at least one second The ionic polymer has a charge density of at least about 0.05 meq / g. 41. The aqueous composition according to claim 1, wherein said at least one second ionic polymer has a charge density of at least about 0.05 meq / g. 42. The aqueous composition according to claim 1, wherein said at least one first ionic polymer has a net anionic charge, said at least one viscosity promoter has a net cationic charge, and the charge ratio between said at minus a first ionic polymer and said at least one viscosity promoter is greater than 1: 1. 43. The aqueous composition according to claim 42, wherein said charge ratio is greater than about 1: 0.6. 44. The aqueous composition according to claim 43, wherein said charge ratio is greater than about 1: 0.4. 45. The aqueous composition according to claim 44, wherein said charge ratio is greater than about 1: 0.3. 46. The aqueous composition according to claim 45, wherein said charge ratio is greater than about 1: 0.
2. The aqueous composition according to claim 46, wherein said charge ratio is greater than about 1: 0.1. The aqueous composition according to claim 1, further comprising at least one sizing agent. The aqueous composition according to claim 48 wherein said at least one sizing agent comprises at least one sizing agent reactive with cellulose. The aqueous composition according to claim 48 wherein said at least one sizing agent comprises at least one alkyl mercane dimer, alkyl methane multimer, succinic acid anhydride, styrene-maleic anhydride, styrene-maleic anhydride copolymer, starch, hydrophobic latex polymer , organic epoxide, acyl halide, fatty acid anhydride, and organic isocyanate. The aqueous composition according to claim 1, which has a gravimetric water retention value that is at least about 10% less than the value of a composition having the same ingredients in the same concentrations but without at least one first ionic polymer or without said at least one second ionic polymer. 52. The aqueous composition according to claim 1, further comprising at least one moderating agent present in an amount effective to prevent the formation of a precipitate or gel, said precipitate or gel comprises an interactive complex of said at least one first polymer ion and said at least one viscosity promoter, said precipitate or gel would be formed in the absence of said moderating agent. 53. The aqueous composition according to claim 52, wherein said at least one moderating agent comprises at least one inorganic salt having a divalent cationic functionality, a carboxylic acid salt, or a starch solution. 54. The aqueous composition according to claim 52 which further has a yield point strength greater than about 10 dynes / cm2. 55. The aqueous composition according to claim 1, further comprising at least one additive comprising at least one of the following: sizing agent; natural, semi-synthetic or synthetic polymer; pigment; clay; filler biocide; surfactant; unsightly agent; antifoam agent; binder; retention aid; and reinforcing agent. 56. The aqueous composition according to claim 1 further including clay. 57. The aqueous composition according to claim 1, further including at least one pigment. 58. The aqueous composition according to claim 57, further including at least one latex colloid. 59. The aqueous composition according to claim 1 which is a surface sizing composition further comprising starch. 60. The aqueous composition according to claim 1, wherein said aqueous composition is a drilling mud for oil field. 61. The aqueous composition according to claim 1, wherein said aqueous composition is a fracturing fluid for oil field. 62. The aqueous composition according to claim 1, wherein said aqueous composition is a water purification composition. 63. The aqueous composition according to claim 62, further comprising at least one surfactant. 64. The aqueous composition according to claim 62, further comprising at least l? ^ É = IT "-? *" and an anti-foam agent. 65. The aqueous composition according to claim 1, wherein said aqueous composition is a retention aid. 66. A procedure for sizing the paper surface, comprising: a) supplying paper; b) applying the aqueous composition of claim 59 on at least one surface of the paper; and c) drying the paper to obtain a paper with a surface ready. 67. A prepared paper made through the process of claim 66. 68. The paper according to claim 67 having a higher level of sizing in accordance with that measured by the Hercules sizing test than a paper sized with a surface sizing composition that is the same but without at least one viscosity promoter. 69. The paper according to claim 67 having a Gurley porosity higher than a paper sized with a surface sizing composition which is the same but which does not have said at least one viscosity promoter. 70. The aqueous composition according to claim 1 which is a paper coating composition further comprising a dÉüAlÉ? lMIlMMl pigment and a latex binder. 71. The aqueous composition according to claim 70 having a gravimetric water retention lower than a paper coating composition that does not contain a viscosity promoter. 72. The aqueous composition according to claim 1 wherein said aqueous composition is a solution. 73. The aqueous composition according to claim 1 wherein said aqueous composition is an emulsion. 74. A process for coating paper comprising: a) supplying paper; b) applying the aqueous composition of claim 1 on at least one surface of the paper and c) drying the paper to obtain coated paper. 75. The coated paper made according to the method of claim 74. 76. A method for reducing the porosity of a porous surface comprising the application of the composition of claim 1 on said porous surface. 77. A coated fibrous sheet obtained by coating a fibrous sheet with the aqueous composition of claim 1. .. «« - a »a--. «S .... ._ .. > .. "_ ^, 78. An aqueous composition prepared by the combination of at least one ionic first polymer, at least one viscosity promoter, and an aqueous medium, said at least one viscosity promoter comprising at least one second ionic polymer having an ionic charge net opposite the net ionic charge of said first ionic polymer, said aqueous composition has a resistance to yield point greater than about 5 dynes / cm2. 79. The aqueous composition according to claim 78, wherein said aqueous composition has a resistance to yield point greater than about 10 dmas / cm2. 80. The aqueous composition according to claim 79, wherein said aqueous composition has a resistance to yield point greater than about 20 dynes / cm2. 81. The aqueous composition according to claim 80, wherein said aqueous composition has a resistance to yield point greater than about 30 dynes / cm2. 82. The aqueous composition according to claim 78, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. dtaa .. ^ .- ^. 83. The aqueous composition according to claim 82, wherein said aqueous composition has a resistance to yield point greater than about 10 dynes / cm 2. 84. The aqueous composition according to claim 83, wherein said aqueous composition has a resistance to yield point greater than about 20 dynes / cm2. 85. The aqueous composition according to claim 84, wherein said aqueous composition has a resistance to yield point greater than about 30 dynes / cm2. 86. The aqueous composition according to claim 78, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. 87. The aqueous composition according to claim 86, wherein said aqueous composition has a yield point strength greater than about 10 dynes / cm2. 88. The aqueous composition according to claim 87, wherein said aqueous composition has a yield point strength greater than about 20 dynes / cm 2. 89. The aqueous composition in accordance with claim 88 wherein said aqueous composition has a resistance to yield point greater than about 30 dynes / cm2. The aqueous composition according to claim 78, wherein said at least one first polymer is a polymer having a net anionic charge and said at least one second ionic polymer is a polymer having a net cationic charge. The aqueous composition according to claim 78 further comprising at least one moderating agent present in an amount effective to prevent the formation of a precipitate or gel, said precipitate or gel comprises an interactive complex of said at least one first ionic polymer and said at least one viscosity promoter, said precipitate or gel would be formed in the absence of said moderating agent. An aqueous composition comprising water, at least a first ionic polymer and at least one viscosity promoter, said at least one viscosity promoter comprising at least one second ionic polymer having a net ionic charge opposite to the ionic charge net of said at least one first ionic polymer, said aqueous composition has a resistance to yield point at least about 10% greater than the yield point strength of a composition having approximately the same viscosity as said aqueous composition, and the same ingredients as said aqueous composition, but without at least one of said at least one first ionic polymer and at least one viscosity promoter. The aqueous composition according to claim 92, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. The aqueous composition according to claim 93, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. The aqueous composition according to claim 92, wherein said aqueous composition has a yield point resistance at least about 50% greater than the yield point resistance of said composition. The aqueous composition according to claim 95, wherein said aqueous composition has a yield point resistance at least about 100% greater than the yield point resistance of said composition. 97. The composition is claimed in accordance with claim 96, wherein said aqueous composition has a yield point strength of at least about 200% greater than the yield point strength of said composition. 98. The aqueous composition according to claim 95, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. 99. The aqueous composition according to claim 98, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. 00. The aqueous composition according to claim 93, wherein said aqueous composition has a yield point resistance at least about 100% greater than the yield point resistance of said composition. 01. The aqueous composition according to claim 96, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. 02. The aqueous composition according to claim 101, wherein said aqueous composition has a lower Brookfield viscosity than », W'T" - approximately 300 cps. 103. The aqueous composition according to claim 95 wherein said at least one first ionic polymer is a polymer having a net anionic charge, and said at least one cationic polymer is a polymer having a net cationic charge. 104. The aqueous composition according to claim 92, further comprising at least one moderating agent for example in an amount effective to prevent the formation of precipitate or gel, said precipitate or gel comprises an interactive complex of said at least a first ionic polymer and said viscosity promoter, said precipitated gel would be formed in the absence of said moderating agent. 105. The aqueous composition according to claim 104, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. 106. The aqueous composition according to claim 105, wherein said composition has a Brookfield viscosity less than about 300 cps. 107. The aqueous composition in accordance with claim 104, wherein said Brookfield composition has a resistance to yield point at least about 20% greater than the yield point resistance of said composition. 108. The aqueous composition according to claim 107, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. 109. The aqueous composition according to claim 104, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. 110. The aqueous composition according to claim 107, wherein said aqueous composition has a yield point resistance at least about 50% greater than the yield point resistance of said composition. 111. The aqueous composition according to claim 110, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. 112. The aqueous composition according to claim 110, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. The aqueous composition according to claim 104, wherein said at least one first ionic polymer is a polymer having a net anionic charge, and said polymer is a cationic polymer is a polymer having a net cationic charge. An aqueous composition comprising water, at least a first ionic polymer and at least one viscosity promoter, said at least one viscosity promoter comprising at least one second ionic polymer having a net anionic charge opposite to the anionic charge net of said at least one first ionic polymer, said aqueous composition has a viscosity greater than the viscosity of a composition having the same ingredients and concentrations of ingredients as said aqueous composition but without any of said at least one first ionic polymer or said at least one viscosity promoter, wherein the concentration of an ingredient is measured as a percentage by weight based on the total weight. The aqueous composition according to claim 114, wherein said aqueous composition has a yield point resistance that is at least 10% greater than the yield strength of said composition. The aqueous composition according to claim 115, wherein said aqueous composition has a yield point resistance that is at least about 20% greater than the yield point resistance of said composition. The aqueous composition according to claim 116, wherein said aqueous composition has a yield point resistance that is at least about 50% greater than the yield point resistance of said composition. The aqueous composition according to claim 114, wherein said at least one first ionic polymer is a polymer having a net anionic charge and said at least one second ionic polymer is a polymer having a net cationic charge. The aqueous composition according to claim 118, wherein said aqueous composition has a yield point resistance that is at least about 10% greater than the yield point resistance of said composition. The aqueous composition according to claim 114, further comprising at least one moderation agent, said at least one agent é¿ * z ¿? * ¿fc¿e 3t.- of moderation is present in an effective amount to prevent the formation of a precipitate or gel, said precipitate or gel comprises an interactive complex of said at least first ionic polymer and said at least one viscosity promoter. The aqueous composition according to claim 120, wherein said aqueous composition has a yield point resistance that is at least about 10% greater than the yield point resistance of said composition. The aqueous composition according to claim 121, wherein said aqueous composition has a yield point resistance that is at least about 20% greater than the yield point resistance of said composition. The aqueous composition according to claim 122, wherein said aqueous composition has a yield point resistance that is approximately 50% greater than the yield point resistance of said composition. The composition according to claim 120, wherein said at least one first ionic polymer is a polymer having a net anionic charge and said at least one second ionic polymer is a polymer having a net cationic charge. the aqueous composition according to claim 124, wherein said aqueous composition has a yield point resistance that is approximately 10% greater than the yield point resistance of said composition. An aqueous composition comprising at least one ionic polymer, at least one viscosity producer, and at least one moderating agent, said at least one ionic polymer having a net ionic charge opposite to the net ionic charge of said at least one viscosity promoter, said at least one moderating agent is present in an amount effective to prevent the formation of a precipitate or gel, said gel precipitate comprises an interactive complex of said at least one first ionic polymer and said at least one viscosity promoter. The aqueous composition according to claim 126, wherein said aqueous composition has a resistance to yield point greater than about 5 dynes / cm 2. The aqueous composition according to claim 126, wherein said aqueous composition has a resistance to yield point greater than about 10 dynes / cm 2. 129. The aqueous composition according to claim 128, wherein said aqueous composition has a yield point strength greater than about 20 dynes / cm 2. 130. The aqueous composition according to claim 129, wherein said aqueous composition has a resistance to yield point greater than about 30 dynes / cm2. 131. The aqueous composition according to claim 126, wherein said aqueous composition has a Brookfield viscosity greater than about 500 cps. 132. The aqueous composition according to claim 131, wherein said aqueous composition has a resistance to yield point greater than about 5 dynes / cm2. 133. The aqueous composition according to claim 132, wherein said aqueous composition has a yield point strength greater than about 10 dynes / cm2. 134. The aqueous composition according to claim 133, wherein said aqueous composition has a yield point strength greater than about 20 dynes / cm2. 135. The composition in accordance with the claim 134, wherein said aqueous composition has a resistance to yield point greater than about 30 dmas / cm2. 136. The aqueous composition according to claim 126, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. 137. The aqueous composition according to claim 136, wherein said aqueous composition has a yield point strength greater than about 5 dynes / cm2. 138. The aqueous composition according to claim 137, wherein said aqueous composition has a yield point strength greater than about 10 dynes / cm2. 139. The aqueous composition according to claim 138, wherein said aqueous composition has a resistance to yield point greater than about 20 dynes / cm2. 140. The aqueous composition according to claim 139, wherein said aqueous composition has a yield point strength greater than about 30 dynes / cm2. 141. The aqueous composition according to claim 126, wherein said at least one first Ionic polymer is a polymer that has a net anionic charge. 142. A method for coating a porous surface, said method comprises applying to said surface an aqueous composition comprising at least a first ionic polymer and at least one viscosity promoter, said at least one ionic polymer having a charge net ionic opposite to the net ionic charge of said at least one viscosity promoter. 143. A method according to claim 142, wherein the aqueous composition has a resistance to yield point greater than about 5 dynes / cm2. 144. A method according to claim 143, wherein the aqueous composition has a Brookfield viscosity less than about 500 cps. 145. A method according to claim 144, wherein the aqueous composition has a Brookfield viscosity less than about 300 cps. 146. A method according to claim 143, wherein the aqueous composition has a yield point strength greater than about 10 dynes / cm2. 147. A method according to claim 145, wherein the aqueous composition has a Brookfield viscosity less than about 500 cps. 148. A method according to claim 147, wherein said aqueous composition has a Brookfield viscosity less than about 300 cps. 149. A method according to claim 146, wherein said aqueous composition has a resistance to yield point greater than about 20 dynes / cm2. 150. A method according to claim 149, wherein said aqueous composition has a Brookfield viscosity less than about 500 cps. 151. A method according to claim 150, wherein said aqueous composition has a viscosity of Brookfield less than about 300 cps. 152. A method according to claim 142, wherein said at least one first ionic polymer has a net ionic charge and said at least one viscosity promoter comprises at least one of a second ionic polymer having a net cationic charge. , and a salt that has a polyvalent functionality. 153. A method according to claim 142, wherein the aqueous composition further comprises a moderating agent that is present in an amount effective to prevent the formation of a precipitate or gel, said precipitate or gel comprises an interactive complex said by at least one first ionic polymer and said at least one viscosity promoter. > - 154. A method according to claim 142, wherein said aqueous composition further comprises a latex colloid. 155. A method according to claim 142, wherein the porous surface is paper. 156. A coated surface produced by the method according to claim 142.