Patent Description:
The present invention defines a process comprising:.

In one aspect the application provides a process comprising:.

In one embodiment the application provides the process wherein the gelatinizing in step a) is by jet cooking.

In one embodiment the application provides the process wherein the solids level of the slurry of step a) is from <NUM>% (w/w) to <NUM>% (w/w) and the jet cooking temperature of step a) is from <NUM> to <NUM>.

In one embodiment the application provides the process wherein the temperature of the slurry in step b) is from <NUM> to <NUM>.

In one embodiment the application provides the process wherein the pH of the cooled slurry in step c) is from <NUM> to <NUM> and waiting until the acidified slurry reaches a funnel viscosity of from about <NUM> seconds to about <NUM> seconds.

In one embodiment the application provides the process wherein the slurry from step c) reacts in step d) with from <NUM>% (w/w on a starch weight basis) to <NUM>% (w/w on a starch weight basis) octenylsuccinic anhydride at a pH of from <NUM> to a pH of <NUM>.

In one embodiment the application provides the process wherein the waxy starch of step a) is a maize or tapioca starch.

In one embodiment the application provides the process wherein the waxy starch of step a) is a maize starch.

In one embodiment the application provides the process wherein the waxy starch of step a) is a tapioca starch.

Native starch granules are insoluble in cold water. When native starch granules are dispersed in water and heated they become hydrated and swell. With continued heating, shear, or conditions of extreme pH, the granules fragment and the starch molecules are dispersed in the water, i.e., made soluble, resulting in a non-granular, dispersed starch. Trksak et al. in <CIT> teaches the preparation of a <NUM>% ("as-is" basis) octenyl succinic anhydride (OSA) dispersed-phase derivatized waxy corn and waxy potato starches. These starches had superior emulsifying properties compared to octenyl succinic anhydride derivatized starches made from granular starches.

<CIT> describes dry composition for the delivery of active agents with good bioavailability, wherein the active agents such as Co-Q10 or lycopene are emulsified using liposome technology and the encapsulated with a modified starch. The modified starch used in <CIT> has been modified to have hydrophilic and hydrophobic groups, e.g. with octenylsuccinic anhydride OSA, and has been degraded with an enzyme to produce short chained saccharides.

<CIT> discloses dextrins for use in the encapsulation of volatile materials such as flavorings, oils, and perfumes as well as nonvolatile materials such as high melting fats. The dextrins in <CIT> are prepared by degrading a waxy maize/ octenyl succinic acid anhydride under acidic conditions and by mixing this dextrin with the material to be encapsulated in water and drying the thus prepared mixture.

Without being bound by theory, it is believed that a starch surface sizing made using a dispersed (cooked) starch reacted with octenyl succinic anhydride has a more uniform distribution of bound octenyl succinic anhydride groups than is possible on a granular starch after reaction of octenyl succinic anhydride. Current octenyl succinic anhydride-reacted and converted starch surface sizes (such as FILMKOTE® <NUM> starch) are not uniformly reacted with octenyl succinic anhydride, as the octenyl succinic anhydride will not react as rapidly with the crystalline regions of the starch granule. The reaction of octenyl succinic anhydride with granular starch results in a product that contains about <NUM>% by weight of un-modified starch that is less effective as surface size than a similar molecular weight OSA-substituted dispersed-phase derivatized starch. Since the reaction of starch with octenyl succinic anhydride requires the emulsification of the octenyl succinic anhydride, the transfer of the OSA into the water phase, and absorption of the OSA from the water into the granular starch, a significant level of hydrolysis of the octenyl succinic anhydride occurs. This results in bound octenyl succinic anhydride levels normally between <NUM>% and <NUM>% from the allowed <NUM>-<NUM>% treatment (based on dry starch weight and a <NUM>-<NUM>% moisture starch). A reaction of octenyl succinic anhydride on a high solids cooked starch provides increased reaction efficiency, since the fully mobile, dispersed starch molecules are more accessible to the octenyl succinic anhydride.

The starch dispersion or cook is advantageously made by non-enzymatic methods of the hydrolysis of starch, such as acid conversion, Manox conversion or shear. These dispersion methods tend to create much less maltose and other low molecular weight oligosaccharides, whose presence greatly increases the likelihood of having starch molecules that are not substituted with octenyl succinic anhydride. Since octenyl succinic anhydride has a molecular weight of <NUM>, this means that each starch molecule will have at least one bound octenyl succinic anhydride group if it has a molecular weight of <NUM> or more (<NUM>+ anhydroglucose units), when treated with <NUM>% octenyl succinic anhydride. In addition to a better control of molecular weight and uniformity of bound octenyl succinic anhydride distribution, a dispersed-phase octenyl succinic anhydride reaction provides higher octenyl succinic anhydride reaction efficiencies than is possible with the reaction of granular starch with octenyl succinic anhydride, leading to bound octenyl succinic anhydride levels above <NUM>% with a <NUM>% treatment (on <NUM>% moisture starch). Because of these factors, a dispersed-phase octenyl succinic anhydride reaction on a converted starch produces a uniformly substituted starch that has a higher bound octenyl succinic anhydride level (due to the higher reaction efficiency of the dispersed-phase reaction), as well as improved surface sizing performance coming from the improved uniformity and higher bound octenyl succinic anhydride level.

Preparation of dispersed-phase derivatized starch by reaction of a fully dispersed, degraded base starch with octenyl succinic anhydride and blending this product as an additive to a low cost (commodity) surface sizing starch cook produces a paper sizing with superior properties. The base starch for the OSA reaction should have a suitable viscosity at ~<NUM>% solids and at <NUM>, which are the OSA/starch reaction conditions. The final product blend may be a liquid natural polymer (LNP). Manufacturing costs are reduced compared to an OSA-reacted granular starch as the starch milk could be directly jet cooked, acid-converted in its dispersed state and reacted with OSA in a process that does not require washing or drying of the base.

The following definitions and abbreviations are used in connection with the processes of the present application unless the context indicates otherwise. The phrase, "converted starch" means starch modified by chemical or physical means to rupture some or all of the starch molecules, weaken some of the granules, and decrease the average size of the starch molecules. A "converted starch" has a reduced viscosity. A "converted starch" can be used at higher concentration, has increased the water solubility, better gel strength, or increased stability. Methods of preparing "converted starch" are found in <NPL>.

The word, "derivatize" means to alter a chemical compound by a chemical reaction with a reagent, such that it adds part or the entire reagent and becomes a derivative. The phrase "dispersed-phase derivatized starch" means starch, which in an at least <NUM> step process, is made sufficiently soluble; then, in the next or any subsequent process step, the starch made sufficiently soluble is derivatized.

FILMKOTE® is a registered trademark of Corn Products Development, Inc. for industrial starch for use in the manufacture of paper.

The term "funnel viscosity" means the results of a viscosity test, measured in seconds, whereby the flow rate of a specific volume of a starch dispersion is measured using a precisely defined glass funnel according to the procedure given in the Examples.

The term "gelatinizating" means a process to change starch and/or starch derivative from a slightly or completely loose granular or comparable granulate form into a form in which stretched starch and/or starch derivative chains are present and those chains are interconnected only slightly, if at all. That is to say, there occurs a transition of starch or starch derivative from a solid form, a colloidal solution, or suspension to a more homogeneous fluid mass. In this application, the term "gelatinizing" is synonymous to terms like "gelling", "gellating", or the like. Such processes are known in the art, for example in "<NPL>.

The phrase, "jet cooking" means providing efficient shearing and heating at <NUM>-<NUM> with direct steam and continuous flow of a material through a combining tube. In jet cooking, high pressure saturated steam, ranging from about <NUM> to about <NUM> psig, is injected through a steam nozzle into the center of a Venturi mixing tube. The slurry mass is pulled into the annulus gap formed by the steam nozzle and Venturi tube opening. The slurry is heated as it accelerates to sonic velocity within the mixing tube. During passage through the mixing tube, the fiber is subjected to extreme turbulence which strips off fiber constituents and ultimately causes fracturing, dissociation, release of soluble biomolecules and refinement/cleansing of insoluble components of the fiber mosaic. Although "jet cooking" conditions may be widely varied by one skilled in the art, conditions are typically those cited in <CIT>. Cooking conditions are in the range from about <NUM> to about <NUM> (<NUM>-<NUM> psig) within the hydroheater portion of the cooker, with a steam line pressure of <NUM>-<NUM> psig entering the cooker. Steam pressure as the hot dispersion leaves the cooker results in an immediate temperature drop in the cooked dispersion to <NUM>. The term "OSA" means octenyl succinic anhydride. Other anhydrides of succinic acids can also be used, such as succinic acid anhydride itself, alkylsuccinic acid anhydrides, or alkenylsuccinic acid anhydrides like decenyl succinic acid anhydride or octenyl succinic acid anhydride.

The phrase, "Manox conversion" means a process for degradation of granular starch, which involves hydrogen peroxide and a manganese salt catalyst such as potassium permanganate in alkaline slurry. Although "Manox conversion" conditions may be widely varied by one skilled in the art, conditions are typically those cited in <CIT>.

The word "sizing" or "size" means a substance that is applied to or incorporated in other material, especially papers or textiles, to act as a protecting filler or glaze. The phrase "sizing agent" means a substance which adheres to substrate fibers and forms a film, with the hydrophilic tail facing the fiber and the hydrophobic tail facing outwards, resulting in a smooth finish that tends to be water-repellent.

The term "starch made sufficiently soluble" means starch that is substantially gelatinized so that the starch does not have a Maltese cross when viewed under polarized light and has lost all of its granular or crystalline structure when viewed microscopically at <NUM>. times magnification. In a more specific embodiment, "starch made sufficiently soluble" means starch having an average particle size of less than one micron, as assessed by Polarization Intensity Differential Plus Elastic Light Scattering (Beckman Coulter LS <NUM><NUM> Aqueous Model).

The phrase "water fluidity" means a viscosity measured on a scale of <NUM> to <NUM> and determined according to the procedure given in the Examples.

The terms "waxy" or "low amylose" means a starch or starch-containing product (herein starch or starch-containing product shall be referred to as starch) containing less than <NUM>% amylose by weight, in one embodiment less than <NUM>% amylose, in another less than <NUM>% amylose, and in yet another embodiment less than <NUM>% amylose by weight of the starch.

The abbreviation "% (w/w)" or percentage weight to weight means concentrations of the ingredients given as a percentage of the weight of an ingredient in hundred weight units of total composition.

The following test procedures were used throughout the examples. Funnel Viscosity Measurement Procedure. The funnel viscosity is determined by adjusting the starch dispersion to be tested to <NUM>% solids level (w/w), as measured by a refractometer. A <NUM> portion of the starch dispersion (anhydrous basis) is weighed into a tarred <NUM> stainless steel beaker containing a thermometer and is brought to <NUM> total weight with distilled water. The sample is mixed and cooled to <NUM>. A total of <NUM> of the starch dispersion is measured into a graduated cylinder. The measured dispersion is then poured into a calibrated funnel while using a finger to close the orifice. A small amount of the dispersion is allowed to flow into the graduate to remove any trapped air, and the starch dispersion remaining in the graduated cylinder is poured back into the funnel. The finger is then removed from the orifice to allow the contents to flow out of the funnel and a timer is used to measure the time required for the <NUM> sample to flow through the apex (junction of the stem and funnel body) of the funnel. This time is recorded and is identified as the funnel viscosity, measured in seconds.

The glass portion of the funnel is a standard <NUM> degree cone angle, thick-wall, resistance glass funnel whose top diameter is from about <NUM> to about <NUM> with the inside diameter of the stem being about <NUM>. The glass stem of the funnel is cut to an approximate length of <NUM> from the apex, carefully fire-polished, and refitted with a long stainless steel tip which is about <NUM> long with an outside diameter of about <NUM>. The interior diameter of the steel tip is about <NUM> at the upper end where it is attached to the glass stem and about <NUM> at the outflow end with the restriction in the width occurring at about <NUM> from the ends. The steel tip is attached to the glass funnel by means of a Teflon tube. The funnel is calibrated so as to allow <NUM> of water to go through in six seconds using the above procedure.

Air Resistance of Paper Measurement Procedure Gurley Density. The instrument is placed so that the outer cylinder is vertical. The outer cylinder is filled with sealing fluid to a depth of about <NUM>, as indicated by a ring on the inner surface of the cylinder. The inner cylinder is raised before inserting the specimen in the test clamp until its rim is supported by the catch. The specimen is clamped between the clamping plates. After the specimen is properly clamped, the inner cylinder is gently lowered until it floats. As the inner cylinder moves steadily downward, the number of seconds, to the nearest <NUM> second, required for the inner cylinder to descend from the <NUM> mark to the <NUM> mark, referenced to the rim of the outer cylinder is measured. Reference is made to Table <NUM> and Table <NUM> for the appropriate correction factors if displacement intervals other than the <NUM> to <NUM> marks are used. The measured time is multiplied by the correction factors from the appropriate table to obtain a corrected result for the alternate interval. If the correction factors are not used, the percentage error related to the measurement interval can be determined from the data in the tables.

Five specimens are tested with the top side up, and five specimens are tested with the top side down.

Water Absorptiveness of Sized Paper Measurement Cobb Test. The specimens are conditioned in an atmosphere in accordance with TAPPI T <NUM> "Standard Conditioning and Testing Atmospheres for Paper, Pulp Handsheets, and Related Products. " Each specimen is weighted to the nearest <NUM>. Half the specimens are tested with the wire side up, the other half with the felt side up. A dry rubber mat is placed on the metal plate and a weighed specimen laid on it. After wiping the metal ring perfectly dry, it is placed upon the specimen, and it is fasten firmly enough in place with the crossbar (or other clamping mechanism) to prevent any leakage between the ring and the specimen. For reporting, the test side is the one that is in contact with the water during the test. A <NUM> volume of water (<NUM> ± <NUM>) is poured into the ring as rapidly as possible to give a head of <NUM> ± <NUM> (<NUM> in. The stopwatch is stared immediately. At <NUM> ± <NUM> seconds before the expiration of the predetermined test period, the water is poured quickly from the ring, taking great care not to drop any of the water upon the outside portion of the specimen. The wing nuts (or other applicable clamping mechanism) is promptly loosened, the crossbar is swung out of the way while holding the ring in position by pressing it down with one hand. Carefully, but quickly, the ring is removed and the specimen is placed with its wetted side up on a sheet of blotting paper resting on a flat rigid surface. Exactly at the end of the predetermined test period, a second sheet of blotting paper is placed on top of the specimen and the surplus water is removed by moving the hand roller once back and once forward over the pad without exerting any additional pressure on the roller. Specimens which exhibit an excess of surplus water after blotting, as shown by glossy areas on the surface, are rejected and the test repeated. The specimen is folded with the wetted area inside. Immediately reweigh it to the nearest <NUM>. The conditioned weight of the specimen is subtracted from its final weight, and is multiplied by <NUM> times the gain in weight in grams to obtain the weight of water absorbed in grams per square meter: weight of water, g/m<NUM> = final weight, g - conditioned weight, g × <NUM>.

Water Fluidity Measurement Procedure. Water fluidity is measured using a Bohlin Visco <NUM> Rotational Viscometer with water jacket (commercially available from Malvern Instruments, Inc. , Southborough, Mass. ), standardized at <NUM> with a standard oil having a viscosity of <NUM> cps. The water fluidity is obtained by determining the viscosity at an <NUM>% solids level and converting that viscosity to a water fluidity (WF) value using the equation below. The procedure involves adding the required amount of starch (e.g., <NUM>. dry basis) to a stainless steel cup and adding <NUM>. distilled water to make a paste. Then <NUM> grams of a <NUM>% CaCl<NUM> solution is added to the cup and the mixture is heated in a <NUM> water bath for <NUM> minutes with rapid stirring for the first <NUM> minutes. The starch dispersion is then brought to the final weight (e.g. <NUM>) with <NUM> or hotter distilled water. The sample is immediately transferred to the viscometer cup, which is then placed into the Bohlin Visco <NUM> unit and analyzed for its viscosity at <NUM> (after the unit is calibrated). The viscosity (in mPas) recorded by the Bohlin Visco <NUM> instrument is converted to a water fluidity number as defined by the following equation: (water fluidity = <NUM> = [<NUM> x Ln(viscosity)]), wherein Ln is the natural logarithm.

Example <NUM>: Preparation of a Degraded Dispersed-Phase Modified Octenyl Succinic Anhydride Waxy Corn Starch. Sample E792:<NUM> was prepared by first slurrying waxy maize starch at <NUM>% solids in tap water. This pH <NUM> slurry was then was jet cooked at approximately <NUM>, resulting in a jet cooked starch dispersion with a dry solids of about <NUM>%. A <NUM> portion of the jet cooked waxy maize starch dispersion was placed in a constant temperature bath and maintained at <NUM> with constant stirring. Concentrated HCl (<NUM>) was added to the jet cook starch slurry to drop the pH to <NUM>. After <NUM> minutes, the funnel viscosity was determined to be <NUM> seconds. The pH was then adjusted to <NUM> with <NUM>% NaOH, the temperature adjusted to <NUM>, and <NUM>% octenyl succinic anhydride was added on starch weight basis ("starch weight" is defined as the weight of starch present, assuming a <NUM>% moisture level of the starch). The pH was maintained at <NUM> for <NUM> hours and then the pH was adjusted to <NUM> with dilute HCL. A <NUM>% level (on starch weight basis) of a preservative was then added to the dispersion. This process was repeated, with samples being made that were acid-degraded to a <NUM> second funnel viscosity and then reacted with <NUM>% and <NUM>% octenyl succinic anhydride (E792:<NUM> and E792:<NUM>).

Example <NUM>: Preparation of a Degraded Dispersed-Phase Modified Octenyl Succinic Anhydride Tapioca Starch. Sample E792:<NUM> was prepared by first slurrying tapioca starch at <NUM>% solids in tap water. This pH <NUM> slurry was then was jet cooked at approximately <NUM>, resulting in a jet cooked starch dispersion with a dry solids of about <NUM>%. A <NUM> portion of the jet cooked waxy maize starch dispersion was placed in a constant temperature bath and maintained at <NUM> with constant stirring. Concentrated HCl (<NUM>) was added to the jet cook to drop the pH to <NUM>. After <NUM> minutes, the funnel viscosity was determined to be <NUM> seconds. The pH was then adjusted to <NUM> with <NUM>% NaOH, the temperature adjusted to <NUM> and <NUM>% octenyl succinic anhydride was added on starch weight ("starch weight" is defined as the weight of starch present, assuming a <NUM>% moisture level of the starch). The pH was maintained at <NUM> for <NUM> hours and then the pH was neutralized to <NUM> with dilute HCI. A <NUM>% level (on starch weight basis) of a preservative was then added to the dispersion. This process was repeated, with samples being made that were second funnel viscosity and then reacted with <NUM>% and <NUM>% octenyl succinic anhydride (E792:<NUM>) and E:<NUM>:<NUM>).

Example <NUM>: Preparation of a Control Octenyl Succinic Anhydride Waxy Corn Modified in the Granular State. Sample E792: <NUM>-<NUM> was prepared by slurrying <NUM> of an acid degraded waxy maize starch at in <NUM> of tap water. The funnel viscosity (measured on a jet cook of this starch as per Example <NUM>) was found to be <NUM> seconds. The pH of this slurry then adjusted to <NUM> with <NUM>% NaOH solution and <NUM>% octenyl succinic anhydride was added on starch weight ("starch weight" is defined as the weight of starch present, assuming a <NUM>% moisture level of the starch). The pH was maintained at <NUM> for <NUM> hours and then the pH was adjusted to <NUM> with dilute HCI. The slurry was then filtered and the collected starch dried.

Example <NUM>: Paper Surface Sizing Evaluation of Dispersed-Phase Modified Octenyl Succinic Anhydride Starches. A surface sizing application test was performed using a laboratory coating unit from Sumet Measurement Technology (Hauser Strasse <NUM>-<NUM>, <NUM> Peiting. , Germany). The coating unit consisted of a single motorized rubber-coated cylinder that was arranged in the format of a horizontal size press where the paper is fed between a flat rubber coated board and the motorized rubber-coated cylinder. The coating pan on the laboratory coater was preheated to <NUM> and a jet-cooked, acid thinned, starch control (approximately <NUM> seconds funnel viscosity) was kept at <NUM> using a water bath before addition into the lab coater. All starch cooks were evaluated at <NUM>%, <NUM>%, or <NUM>% solids and <NUM>, in order to vary their pickup levels on the paper. The octenyl succinic anhydride-modified starches were blended with the acid-thinned control starch at a weight ratio of <NUM>:<NUM> (acid-thinned starch:octenyl succinic anhydride starch) and mixed for <NUM> minutes using a motorized stirrer at <NUM> rpm before evaluation. The acid-thinned control starch was evaluated without blending at <NUM>%, <NUM>%, or <NUM>% solids.

A <NUM> x <NUM> sheet of <NUM>/m<NUM> paper base stock was pre-weighed after conditioning in a <NUM> and <NUM>% relative humidity room. The motorized rubber-coated cylinder was set to a <NUM> meters/min. A sample of <NUM> starch was poured into the coating pan and the thickness of starch on the motorized rubber-coated cylinder was controlled via a pressure regulating rod set to <NUM> Newtons. The paper sheet was held on the flat rubber coated board and fed between the motorized rubber-coated cylinder and another non-motorized rubber coated cylinder. A cylinder pressure of <NUM> Newtons was applied on the non-motorized rubber coated cylinder. After the stock paper was passed through the cylinders, primary drying was done immediately with an online infra-red heater set at <NUM>%. Secondary drying was subsequently done on the mirror-faced surface of a Formax drum dryer (Adirondack Machine Corporation, <NUM> Dixon Road, Queensbury, NY <NUM> USA) set to <NUM> rpm at <NUM>. The sheets were then reconditioned in a <NUM> and <NUM>% relative humidity room and weighed again to determine the amount of surface-size starch (the percentage pickup in g/m<NUM>) that was applied on the sheet. These sheets were then tested for their air permeability (porosity) using Gurley density tester. This unit develops porosity values according to a TAPPI Standard Method (T460 om-<NUM>, air resistance of paper (Gurley method), TAPPI Press, Atlanta, Ga. The porosity values in Table <NUM> are the times (average of <NUM> sheets) required for <NUM><NUM> of air to flow through a <NUM><NUM> area of the sheet. The values were then plotted and a software package (Mini Tab) was used to fit a line to the data to allow estimation of Gurley density values at a <NUM>/m<NUM> and <NUM>/m<NUM> pickup for each additive.

Example <NUM>: Paper Surface Sizing Comparison of Dispersed-Phase Modified Octenyl Succinic Anhydride Starches with Granular Reacted Equivalents. An additional a jet cooked starch dispersion with a funnel viscosity of <NUM> seconds (E792: <NUM>-<NUM>) was prepared as per Example <NUM>. This was reacted with <NUM>% octenyl succinic anhydride on starch weight basis. In a similar manner, an additional control octenyl succinic anhydride waxy com starch (E792:<NUM>-<NUM>), modified with <NUM>% octenyl succinic anhydride (on starch weight basis) in the granular state, was made as per Example <NUM>. These were evaluated as per Example <NUM> except that a <NUM>/m<NUM>, non-surfaced fine paper base stock was used. These sheets were also tested for sizing according to a TAPPI Standard Method (T441 om-<NUM>, "<NPL>. Results are listed in Tables <NUM> and <NUM>. The Gurley density or Cobb values were plotted against their g/m<NUM> pickups and values at <NUM>/m<NUM> and <NUM>/m<NUM> were estimated by the same procedure used in Example <NUM>.

While the <NUM>:<NUM> blend of <NUM>% octenyl succinic anhydride granular surface size gave Gurley density values (higher is better) that were <NUM>% of the <NUM> water fluidity tapioca control, the equivalent blend of the dispersed-phase <NUM>% octenyl succinic anhydride surface size gave <NUM>% (<NUM>% better). Increasing the octenyl succinic anhydride to <NUM>% increased these values to <NUM>% and <NUM>%, with the dispersed-phase octenyl succinic anhydride reaction being <NUM>% better than the granular octenyl succinic anhydride reaction product. Cobb sizing (lower values are better) improved even more. The <NUM>:<NUM> blend of <NUM>% octenyl succinic anhydride granular surface size gave <NUM>% of the <NUM> water fluidity tapioca control (i.e. <NUM>% of the water pickup of the control). The equivalent blend of the dispersed-phase <NUM>% octenyl succinic anhydride surface size gave <NUM>% of the control (only <NUM>% of the water pickup of its granular equivalent). Increasing the octenyl succinic anhydride to <NUM>% increased these values to <NUM>% and <NUM>% of the control, with the dispersed-phase octenyl succinic anhydride reaction allowing only <NUM>% of the water pickup of its granular equivalent. The dispersed-phase octenyl succinic anhydride product exhibited significantly lower Cobb pickups and higher Gurley density values than the equivalent granular product.

Example <NUM>: Paper Surface Sizing of Dispersed-Phase Modified Octenyl Succinic Anhydride Starches at Varying Ratios on Acid Thinned Tapioca. The <NUM>% octenyl succinic anhydride dispersed-Phase modified starch was also evaluated at <NUM>:<NUM> and <NUM>:<NUM> ratios (blended with the acid-thinned control starch). These were evaluated as per Example <NUM>, except that a <NUM>/m<NUM>, non-surface sized fine paper base stock was used. Results are listed in Tables <NUM> and <NUM>. The measured properties (Gurley density or Cobb sizing) was plotted against the g/m<NUM> pickup and values interpolated at <NUM>/m<NUM>and <NUM>/m<NUM> pickups for each additive by the method given in Example <NUM>.

Increasing the amount of dispersed-phase octenyl succinic anhydride product on <NUM> water fluidity tapioca increased Gurley density values from <NUM>% of the <NUM> water fluidity tapioca control at a <NUM>% add-on to <NUM>% at a <NUM>% add-on. The values for a <NUM>:<NUM> blend of the granular <NUM>% octenyl succinic anhydride type are shown for comparison.

Cobb sizing improved in a similar manner. With a <NUM>% add-on of the <NUM>% octenyl succinic anhydride dispersed-phase surface size, the Cobb sizing was improved by <NUM>% compared to the <NUM> water fluidity tapioca control. Increasing this to <NUM>% and <NUM>% improved Cobb by <NUM>% and <NUM>% respectively. Even a <NUM>% add-on of the dispersed-phase <NUM>% octenyl succinic anhydride product exhibited not only a <NUM>% higher Gurley density value, but a <NUM>% lower Cobb pickup than the control. Its Cobb value was similar at the <NUM>% add-on to a <NUM>% add-on of the <NUM>% octenyl succinic anhydride granular product.

Example <NUM>: Preparation of a Degraded Dispersed-Phase Modified Octenyl Succinic Anhydride Waxy Corn Starch. This was prepared by slurrying waxy corn starch at <NUM>% solids, and jet cooking this slurry at <NUM>. The cooked starch (about <NUM>% solids), was allowed to cool to <NUM>. Hydrochloric acid (<NUM>% on starch cook, pH <NUM>) was added and the viscosity tracked for <NUM> minutes until an <NUM>% funnel viscosity time of <NUM> seconds was observed. The starch cook was then adjusted to pH <NUM>, <NUM>% octenyl succinic anhydride (on starch weight basis) was added, and <NUM> of <NUM>% NaOH solution was used to maintain the pH at <NUM> until the pH was stable (about <NUM> hours). The bound OSA content was <NUM>%.

The reaction mixture was then added at a <NUM>% level to a jet cooked, <NUM> water fluidity, acid converted, tapioca starch and used to surface size paper at <NUM> different total solids levels (<NUM>%, <NUM>%, <NUM>%) at <NUM> to vary the amount of starch applied to the paper. At a starch pickup level of <NUM>/m<NUM>, a low pressure Gurley density porosity reading of <NUM> seconds was obtained, which is twice that of the jet cooked, <NUM> water fluidity, acid converted, tapioca starch alone. Under the same reaction conditions and starch application level, a <NUM>% OSA reaction on a similar viscosity granular base waxy starch (FILMKOTE® <NUM> starch, <NUM>% bound OSA) gave only a <NUM> seconds Gurley density reading.

Thus, the dispersed-phase derivatized starch with <NUM>% OSA containing liquid natural polymer was over <NUM> times as effective as the comparable granular reaction product, while it contained only about <NUM> times the bound OSA. When added at a <NUM>% level onto the <NUM> water fluidity tapioca starch, FILMKOTE® <NUM> starch gave no liquid natural polymer improvement at a <NUM>/m<NUM> pickup (see <FIG>).

Example <NUM>: Comparison of Paper Surface Sizing of Dispersed-Phase Modified Octenyl Succinic Anhydride Waxy Corn Starch with Granular Reacted Equivalents. A jet cooked starch dispersion with a funnel viscosity of <NUM> seconds was prepared as per Example <NUM>. This was reacted with either <NUM>% or <NUM>% octenyl succinic anhydride (on starch weight basis). In a similar manner, control octenyl succinic anhydride waxy com starch, modified with either <NUM>% or <NUM>% octenyl succinic anhydride (on starch weight basis) in the granular state, was made as per Example <NUM>. All starch cooks were evaluated at <NUM>%, <NUM>%, or <NUM>% solids in order to vary their pickup levels on the paper. The octenyl succinic anhydride-modified starches were blended with the acid-thinned tapioca starch at a weight ratio of <NUM>:<NUM> (acid-thinned starch:octenyl succinic anhydride starch) and mixed for <NUM> minutes using a motorized stirrer at <NUM> rpm before evaluation. These were evaluated as per Example <NUM> except that a <NUM>/m<NUM>, non-surface-sized fine paper base stock was used. Results are listed in Table <NUM>. The measured properties (Gurley density or Cobb sizing) were plotted against the g/m<NUM> pickup and values interpolated at <NUM>/m<NUM>and <NUM>/m<NUM> pickups for each additive by the method given in Example <NUM>. The comparison of the sizing properties of the dispersed-Phase modified and granular reacted acid-thinned tapioca starch:octenyl succinic anhydride starch blend is given in Table <NUM>.

The raw data for the Gurley density measurements are given in Table <NUM>. In the Gurley density test, a higher value is better.

The raw data for the Cobb water absorption measurements are given in Table <NUM>. In the Cobb water absorption test, a lower value is better.

Example <NUM>: Comparison of Paper Surface Sizing of Dispersed-Phase Modified Octenyl Succinic Anhydride Waxy Corn Starch at Different OSA Loadings. A jet cooked starch dispersion with a funnel viscosity of <NUM> seconds was prepared as per Example <NUM>. This was reacted with <NUM>%, <NUM>%, or <NUM>% octenyl succinic anhydride on starch weight. All starch cooks were evaluated at <NUM>%, <NUM>%, or <NUM>% solids in order to vary their pickup levels on the paper. The octenyl succinic anhydride-modified starches were blended with the acid-thinned tapioca starch at a weight ratio of <NUM>:<NUM> (acid-thinned starch:octenyl succinic anhydride starch) and mixed for <NUM> minutes using a motorized stirrer at <NUM> rpm before evaluation. These were evaluated as per Example <NUM>, except that a <NUM>/m<NUM>, non-surface-sized fine paper base stock was used. Results are listed in Table <NUM>. The measured properties (Gurley density or Cobb sizing) were plotted against the g/m<NUM> pickup and values interpolated at <NUM>/m<NUM>and <NUM>/m<NUM> pickups for each additive by the method given in Example <NUM>. The comparison of the sizing properties of the dispersed-Phase modified and granular reacted acid-thinned tapioca starch:octenyl succinic anhydride starch blend is given in Table <NUM> along with the results from a non-blended acid-thinned tapioca starch control.

Example <NUM>: Comparison of Paper Surface Sizing of Dispersed-Phase Modified Octenyl Succinic Anhydride Waxy Corn Starch at Different Blend Ratios. A dispersed-phase modified <NUM>% octenyl succinic anhydride starch was prepared as per Example <NUM>. All starch cooks were evaluated at <NUM>%, <NUM>%, or <NUM>% solids in order to vary their pickup levels on the paper. The octenyl succinic anhydride-modified starch was blended with the acid-thinned tapioca starch at a weight ratios of <NUM>:<NUM>, <NUM>:<NUM>, and <NUM>:<NUM> (acid-thinned starch:octenyl succinic anhydride starch) and mixed for <NUM> minutes using a motorized stirrer at <NUM> rpm before evaluation. These were evaluated as per Example <NUM> except that a <NUM>/m<NUM>, non-surface-sized fine paper base stock was used. Results are listed in Table <NUM>. The measured properties (Gurley density or Cobb sizing) were plotted against the g/m<NUM> pickup and values interpolated at <NUM>/m<NUM>and <NUM>/m<NUM> pickups for each blend by the method given in Example <NUM>. The comparison of the sizing properties of the acid-thinned tapioca starch:dispersed-phase modified octenyl succinic anhydride starch blend is given in Table <NUM> along with the results from a non-blended acid-thinned tapioca starch control.

Claim 1:
A process comprising:
a) slurrying a waxy starch and gelatinizing the slurry, wherein waxy means a starch or starch-containing product containing less than <NUM> % amylose by weight;
b) optionally cooling the slurry;
c) acidifying the optionally cooled slurry and waiting until the acidified slurry reaches a funnel viscosity of from <NUM> seconds to <NUM> seconds;
d) reacting the slurry from step c) with octenyl succinic anhydride;
e) mixing the reacted slurry with converted starch, wherein converted starch means starch modified by chemical or physical means to rupture some or all of the starch molecules, weaken some of the granules, and decrease the average size of the starch molecules; and
f) applying the starch mixture to paper.