JPH0255702A - Modified starch emulsifier having a stable keeping quality - Google Patents

Abstract

PURPOSE: To obtain a modified starch having emulsifying property of emulsion which shows improved stability, oiling resistance, and gelling resistance during storage by decomposing a pasted starch derivative with an in-vivo enzyme up to a specified quantity to form maltose.

CONSTITUTION: A pasted starch derivative having respective substituents containing hydrophobic group, or hydrophilic group and hydrophobic group is prepared, and up to 70wt.% of the starch derivative is decomposed with an in-vivo enzyme capable of cleaving 1,4-α-D-glucocide bond from non-reduced terminal of starch but not cleaving 1,6-α-D-glucocide bond of starch (e.g.; β- amylose) to form maltose, whereby a modified starch having emulsifying property of emulsion which shows improved stability, oiling resistance and gelling resistance during storage is manufactured.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to modified starch. The starch is useful in shelf-stable emulsions, especially flavored oils, in systems requiring stable oil-in-water emulsions.
For example, it is useful as a replacement for gum arabic in beverages flavored with citrus oils. Furthermore, the present invention relates to a method for producing modified starch and to chemical compositions, foods and beverages containing modified starch.

Various chemical compositions are used as emulsifiers in the food, cosmetics, paint, pharmaceutical and polymer industries as well as in textile and leather processing, flotation, oil drilling and agricultural spraying operations. In many of these uses, the emulsifier also acts as a stabilizer for the viscosity or fluidity of the continuous phase. Often this use requires that the emulsion be storage stable for long periods of time.

Typical compositions that act as water-soluble emulsifiers and stabilizers include guar gum, acacia and other gums, starches, proteins, various water-soluble polymers and their congeners. For example, the Encyclopedia of Chemical Medicine
f Chemical Technology),
Edited by Kirk Osmer, 3rd edition, Wily-Intersiene, New a
See Ivy, New York, 1979, Vol. 8, pp. 900-910, pp. 918, pp. 923-925 and Vol. 12, pp. 55-56. Gum arabic is preferred in many uses because of its storage stability, particularly during cooling or frozen storage of emulsions.

Gum arabic is a branched substituted heteropolysancalide that is highly water soluble, low viscosity and odorless, colorless or tasteless. Gum arabic is used as an emulsifier and stabilizer in foods such as confections, syrups, flavored oil emulsions, ice creams and beverages, and in inks, adhesives, textile materials and lithographic solutions.

Gum Arabic is a naturally occurring rubber sourced from Central East Africa. Since gum arabic is obtained from this region, it is expensive and its supply and quality are unpredictable, so the industry is looking for a cheap alternative to gum arabic that is shelf-stable for a long time, and products derived from starch are It has been proposed for various uses.

1953 by Caldwell et al.
U.S. Patent No. 2,661,34, issued December 1,
No. 9 describes substituted dicarboxylic anhydride starch half ester derivatives. Some of these derivatives form stable oil-in-water emulsions suitable for use in beverage emulsions, flavor emulsions and other emulsions. For example, P,) Rubiano (T
Rubiano, Chapter 9, Modified Starches: Properties and Uses, CRC Press, BocaRaton
), Florida, 1986, pp. 134-147. Cold water soluble, low viscosity octenyl succinate starch derivatives have been successfully used to replace gum arabic in carbonated beverages. Relatively high viscosity octenyl succinate derivatives are useful as gum arabic substitutes in salad dressings. Such substituted dicarboxylic acid starch half ester derivatives are also used in place of gum arabic to encapsulate hydrophobic substances such as flavors, vitamins, aromas and oils. Gabcell encapsulations are commonly prepared by spray drying oil-in-water emulsions. Some variations of this capsule encapsulation result in compositions that result in gradual or limited release of the encapsulated flavor or oil. Other materials can be dissolved in water with higher solids content than gum arabic equivalents and are superior to gum arabic in certain uses.

Low viscosity (chemical) starches used in beverages and flavor emulsions are usually produced by acid-lysis of starch. Methods for producing low viscosity starches are well known.

7, 1977 by Richards et al.
No. 4,035,235, issued May 12, discloses a process for the degradation of lipophilic substituted starches, which uses alpha-amylase digestion as an alternative to acid-digestion of low viscosity starches. used in the manufacture of Lipophilic substituted starches are suitable for flavor encapsulation and oil-in-water emulsions. This process produces a starch product suitable for use in oils as emulsifiers and encapsulating agents in beverages. One disadvantage of using known starch derivatives in place of gum arabic is that known starch derivatives are not very stable during storage. This starch derivative exhibits a shorter shelf life and worse cooling and freeze/thaw stability compared to gum arabic and is therefore used in certain applications, such as flavored syrups used in the production of soft drinks and similar types of beverages. At base, this starch-derived substitute does not behave as well as gum arabic. Beverage manufacturers transport flavored syrup bases to bottlers in different regions, where they are placed in long-term cooled storage before being used in bottling operations, so that the flavored oil emulsion remains stable during storage. There must be. Furthermore, since the cooling temperature varies from bottler to bottler or from day to day, flavored oil emulsions may be frozen/
Must be able to withstand temperature cycling, including thawing cycles.

Stability problems in beverage use are believed to arise because starch products exhibit a tendency to age and do not subject flavored oil emulsions to temperature cycling or long-term storage. In severe cases, starch ages and forms a gel;
The flavor oil separates completely from the aqueous phase. Starch retrogradation is essentially a crystallization process. This occurs when the linear portions of the starch molecule itself, adjacent to each other, form interchain hydrogen bonds with the hydroxyl groups.

When a molecule develops enough interchain hydrogen bonds, it is accompanied by the formation of molecular aggregates. This aggregate exhibits a reduced capacity for hydration and therefore low water solubility. This aggregate precipitates or forms a gel in a thick solution. The tendency to retrograde is more pronounced in starches containing high levels of linear amylose molecules. The tendency towards retrogradation is less pronounced in starches containing linear (amylose) and branched (amylopectin) or only branched molecules. As the temperature decreases, starches containing amylose and amylopectin exhibit a greater tendency to retrograde.

Retrogradation can be partially overcome in certain applications by chemically derivatizing starch molecules, interfering with the association between starch molecules or between parts of the same molecule, thereby improving the hydration capacity of starch during storage. Stabilizes starch by reducing its tendency to lose. For example, starch is reacted with reagents to introduce substituents, such as hydroxypropyl, phosphate, acetate or succinate groups, to stabilize the starch molecule during storage. This derivatization reaction is carried out on starches that are further modified by cross-linking or decomposition to obtain starches for special applications. However, this derivatized starch does not produce the stable emulsifying properties typical of gum arabic.

Other known methods of limiting starch retrogradation at low temperatures also include:
Does not produce stable emulsified starch. For example, U.S. Pat. No. 3,525,672 issued Aug. 25, 1970 by Wurzburg et al. are disclosed to provide freeze/thaw stability to pie fillings, puddings and other thickened food products exposed to low temperature storage. In addition to the inhibitory treatments described, it has sometimes been stated that it is advantageous to partially derivatize the starch base. Typical substituents include ester groups such as acetate,
Mention may be made of succinate, phosphate and sulfate groups as well as ether groups.

U.S. Pat. No. 4,428,972, issued Jan. 31, 1984, by Wurzberg et al., discloses waxy starch thickeners with improved low temperature stability in aqueous dispersions. There is. The starch is obtained from selected -X5UZ gene plants.

However, with respect to overcoming low temperature storage compromise, this invention does not disclose any starch products useful for producing shelf-stable oil-in-water emulsions. Thus, there remains a need for a product that has emulsifying properties that combine quality during storage, cooling and freeze/thaw cycles and that can be used in place of gum arabic.

There is therefore a need for an improved modified starch that exhibits the stable emulsifying properties of gum arabic. According to the present invention, such modified starch is provided together with a method for producing such modified starch.

Products containing starch-based emulsions, in particular flavored oil emulsions, having good storage stability are also provided.

The present invention consists of a starch derivative containing a hydrophobic group or a hydrophilic group and a hydrophobic group, up to 70% of which can cleave the 1,4-α-D-glucoside bond from the non-reducing end of the starch. , an emulsion that is degraded by in vitro enzymes that are unable to cleave the 1,6-α-D-glucosidic bonds of starch and exhibits improved stability, oiliness and gelation resistance during storage. Provides a modified starch with properties.

The invention further comprises the steps of: a) producing a gelatinized starch derivative, which derivative is characterized by a respective substituent containing a hydrophobic group or a hydrophilic group and a hydrophobic group; b) within the starch derivative An in vitro enzyme that can cleave up to 70% by weight of the 1,4-α-〇-glucoside bond from the non-reducing end of starch, but is unable to cleave the 1,6-α-Ω-glucoside bond of starch. A process for producing a modified starch having the emulsifying properties of an emulsion exhibiting improved stability and resistance to oiling and gelling during storage, comprising decomposition of the modified starch to maltose.

The enzymatic treatment used in the method of the invention is carried out after the starch has been derivatized to contain either hydrophobic groups or both hydrophilic and hydrophobic groups and has emulsifying properties.

Alternatively, enzymatic treatment is carried out before producing the starch derivative. A method for producing such derivatives is disclosed in the aforementioned US Pat. No. 2,661,349. Preferred starch derivatives are starch alkenyl succinate half esters in which the carboxyl group is present as an acid or carboxilade salt. However, it is stated that such modified starches can be produced using any method that produces the desired hydrophobic functionality or both hydrophobic and hydrophilic functionality in the starch molecule, thereby producing emulsifying properties. There is. Suitable derivatives and methods of making them are described in US Pat. No. 4,626,288, issued Dec. 2, 1986, by Trzasko et al.

The 1,4-α-D-glucoside bond can be cleaved from the non-reducing end of the starch molecule;
．． Up to 70% by weight (preferably 55% by weight) of starch derivatives containing hydrophobic groups or hydrophilic and hydrophobic groups are degraded by treatment with in vitro enzymes that cannot cleave 6-α-D-glucosidic bonds. and continue until it becomes maltose.

In producing the modified starch of the present invention, the desired starch is slurried in water in the proportion necessary to achieve the desired enzyme-group 'ft t14 degrees or in a proportion calculated to be suitable for end use. do. If desired, starch is used in granular form, but enzymatic degradation of granular starch proceeds gradually. The temperature and pH of the mixture are then adjusted to optimal conditions for the particular enzyme used to produce the starch product recommended by the manufacturer or supplier.

The enzyme can cleave the 1,4-α-D-glucoside bond from the non-reducing end of the starch molecule, but it must be an in vitro enzyme that cannot cleave the 1,6-α-D-glucoside bond of the starch molecule. Must be.

Beta-amylase - which is preferred - is a very specific biological enzyme, by its action only from the non-reducing end of the starch molecule with a maltoside group that binds to the glucose group via a 1,4-α-D glucosidic bond. Reactive complex compounds can be formed.

Thereby, the enzyme attacks the starch only at the non-aldehyde end (non-reducing end) and separates the maltose units from this outer branch until the branch point (1,6-linkage) is reached. A single maltose or glucose unit is
After enzymatic treatment, it remains at each branch point of the starch molecule. This in vitro enzyme can separate the 1,4-bonds of starch branches, but cannot break down the 1,6-bonds, so the remainder of this degradation process is a tightly packed branched structure, which is essentially No superolateral branches or contains only short lateral branches. This product is therefore free of long outer chains which clearly result in retrogradation and syneresis in aqueous starch dispersions exposed to long-term storage and/or repeated freeze/thaw cycles.

The enzyme is starch 70% by weight (preferably 55% starch)
Digest the starch until it decomposes to maltose, or until the desired end point is reached (i.e., sufficient decomposition to provide improved storage stability for special emulsions made with starch). be able to.

The end point is determined by the change in viscosity, by the reducing sugar content or by all other known methods for determining the amount of enzymatic degradation of starch molecules. Alternatively, enzymatic degradation may continue until substantially all of the resulting maltose units have been removed from the starch molecule. Typically, decomposition is carried out for periods ranging from several hours to 24 hours or more, depending on temperature, enzyme and group concentrations, and other changes. The enzymatic degradation is then terminated by heat, chemical addition, or other known methods for inactivating or separating the enzyme from its substrate.

The resulting degraded starch composition is spray dried, drum dried, or otherwise recovered in a form suitable for the present invention.

It is understood that the present invention encompasses all emulsifying compositions in which the emulsifier is a starch, the starch being modified by enzymes to improve the storage stability of the emulsion. Emulsions consisting of mixtures of modified starches and gums or other emulsifiers must therefore be included.

Use of the modified starch of the invention in products in which gum arabic is used as an emulsifier, stabilizer or congener thereof and in products in which polymeric water-soluble emulsifiers are used to form or stabilize emulsions. is advantageous. It can therefore be used in beverages flavored with oils, such as orange or lemon oil, confectionery, ice cream, other beverages requiring shelf-stable emulsifiers and other food products. Can be used in water and alcohol-based beverages. It can also be used in the production of flavored oils where the starch is reconstituted with water to form a flavored emulsion and in the production of flavored oils and in inks, textile materials and other non-food end uses.

Suitable starches used in the production of enzymatically degraded starches according to the invention are of all botanical origin, including corn, potato, sweet potato, wheat, rice, sago, tapioca, bollard, turgium and its congeners; derived from. Also included are chemically engineered products derived from any of the above starches. For example, oxidation, α-
Mention may be made of free-flowing or weakly boiling starches and derivatized starches, such as ethers and esters, produced by amylase modification, mild acid hydrolysis or thermal dextrinization.

The starch is preferably a gelatinized starch (preheat-treated non-granular starch), and may also be a fluid starch modified by mild acid decomposition or known thermal dextrinization methods.

(For example, M, W, Ru tenber
g), 'Starch and its chemical processing', Water-soluble gums and resins - Handbook, R, L, Davids
on), editor, McGra-Hill (McGra-formerly f.
l), Inc., New York, New York 19
1980, pp. 22-36). This chemical technology 1
Or use several combinations. Chemical engineering is hydrophobic/hydrophilic (
or simply hydrophobic) agents and before β-amylase treatment.

If desired, the starch is modified by treatment with an alpha-amylase enzyme to produce a fluid starch as described in U.S. Pat. No. 4,035,235. α−
Chemical modification with amylase is also commonly performed prior to β-amylase treatment. If a high viscosity emulsion system is desired, there is no need to modify the starch.

The starch is derivatized by treatment with all agents that impart emulsifying properties to the starch. Derivatization is performed before or after β-amylase treatment. The reagent must have a hydrophobic portion and may contain a hydrophilic portion. The hydrophobic moiety is an alkyl-, alkenyl-, containing at least 5, preferably from 5 to 24 C-atoms.
It must be an aralkyl or aralkenyl group.

As in the preferred embodiment below, the hydrophilic moiety is provided by an agent, or as in other embodiments, the hydroxyl groups of the starch itself act as the hydrophilic moiety and the agent provides only the hydrophobic moiety. .

In a preferred embodiment, the starch is
1.349 by reaction with an alkenyl cyclic dicarboxylic acid anhydride. However, any method of derivatizing starch that produces the desired mixture of hydrophobic and hydrophilic functions in the starch molecule, thereby producing stable emulsifying properties, can be used to produce the modified starch according to the invention. Can be done. This involves a previously unknown method.

If a low viscosity emulsifier is desired, a preferred example is an amylopectin-containing starch, such as the octenyl succinate half ester derivative of waxy corn. It is engineered to have a water fluidity of up to about 60. Water flow rate is an empirical test of viscosity measured on a scale of 0-90. In this case, fluidity is the reciprocal of viscosity. The water fluidity of starch is generally measured using a Thoma large rotational shear type viscometer (Arthur H).

Thomas, Inc., Philadelphia, PA). This meter has a viscosity of 24.
Standardized using a standard oil with 73 cps. This oil requires 100 revolutions of 23.12±0.05 seconds. Accurate and reproducible measurements of water fluidity are obtained by determining the elapsed time for 100 revolutions at various solids levels depending on the degree of modification of the starch (as the modification increases, the viscosity decreases). In a preferred embodiment, the modified starch is treated with anhydrous octenyl succinate at least 0.25% and preferably 3.0%. If desired, hydroxypropyloctenyl succinate derivatives can be used.

For other products, the degree or level of substitution that yields the desired viscosity and emulsification properties is used. For example, US Pat. No. 4,035,235 discloses a suitable embodiment. It consists of a process for producing lipophilic derivatives of starch that are used as a replacement for gum arabic for encapsulating water-insoluble substances such as volatile flavor oils and perfumes.

In a preferred embodiment, the next step after the production of the starch derivative is to gelatinize the derivatized starch. The gelatinization process unfolds the starch molecules from their granular structure, allowing enzymes to more easily and uniformly break down the outer branches of the starch molecules. After gelatinizing the starch-based slurry, the slurry solids, temperature, and pH are adjusted to produce optimal enzyme activity.

Optimal parameters for enzyme activity will vary depending on the enzyme used. The rate of enzymatic degradation therefore depends on factors such as the type of enzyme used, enzyme concentration, substrate concentration, pH 1 temperature, presence or absence of inhibitors, and other factors. Depending on the type of enzyme, ie its origin, various parameters need to be adjusted to achieve optimal digestion rates. Generally preferred enzymatic digestion reactions are performed at maximum solids content. The rate is such that the subsequent drying of the starch composition can be facilitated while maintaining an optimal reaction rate. For the barley β-amylase used according to the invention for producing emulsifiers for applications in beverages, for example, preheat-treated starch dispersions with a solids content of up to 33% are preferred. However, the more solids used, the more difficult or ineffective stirring becomes with more solids, and the more difficult the starch dispersion becomes to handle.

While the method of the invention has been described using β-amylase as the enzyme component, other enzymes such as in vitro-α-1,
4-glucosidase, in vitro-1,4-α-D-glucan maltotetrahydrolase, in vitro-1,4-α-D
- Glucan maltohexahydrolase or selectively cleaves the 1,4-bond of starch molecules from the non-reducing end,
1.6- Other biological enzymes with intact bonds are used to produce modified starches according to the invention.

Because these in vitro enzymes only separate glucose, maltose, or larger saccharide units from the outer branches of the amylopectin molecule and do not debranch them, enzymatic degradation methods leave short chain branch points intact. give rise to molecules. In amylopectin, the branch point is approximately 4 monosancalide units of the molecule.
Occurs in ~5%. If enzymatic degradation of amylopectin continues, the outer branches of the molecule will be shortened to the point that they reduce or eliminate association with other branches, and the remaining l,6-branch points will associate the inner branches. protect from The degraded molecules therefore exhibit improved aging resistance during storage and during freeze/thaw cycles. For this reason, an in vitro enzyme that is capable of cleaving 1,4 bonds but not cleaving 1,6 bonds from the non-reducing end of starch molecules is an essential requirement of the present invention.

Although the method of the present invention uses enzymes in solution, methods using enzymes supported on solid supports are suitable for use in the present invention.

Optimal concentrations of enzyme and substrate are limited by the level of enzyme activity. Enzyme activity is expressed in aqueous enzyme solution - diastase power (DP''). DP' is the amount of enzyme contained in a 5% solution of the sample enzyme preparation. When incubated with substrate 100d for 1 hour at 20°C, it produces sufficient reducing sugars to reduce Fehling's solution 5W11.
Codex), 3rd edition, National Academy Bulletin,
Washington, D.C., 1981, p. 484.

An excess of 334 DP' per 100 g starch per dry weight means that gelatinized starch solutions containing up to 33% solids must be broken down within 8 hours under optimal conditions of temperature and pH.
”840-1.110 (at pH 5.3 and temperature 57°C) is preferred.

This reaction proceeds in the presence of a buffer to ensure that p)l is at optimal levels during degradation. Buffers such as acetate, citrate or other salts of weak acids are advantageous. Other reagents can be used for optimal enzyme activity. The reaction is carried out at 55-60°C at a pH range of about 3-10, preferably 5-7, most preferably 5.7.

Aqueous starch dispersion at 20-100℃, preferably 55℃
A temperature of -60°C, most preferably 57°C, must be maintained during the enzymatic digestion. However, if relatively short reaction times are desired, temperatures in the range of 60-63°C or even higher enzyme concentrations are used. With other parameters of the enzymatic reaction, preferred and optimal temperatures will vary with changes in other parameters, such as substrate concentration, pH, and other factors governing enzyme activity, and can be determined by the practitioner.

The enzymatic reaction can be continued until the desired level of degradation is reached or until substantially all of the resulting maltose is removed from the starch molecules. The progress of the enzymatic reaction is measured by various methods. If all critical parameters are verified for achieving a particular starch composition, then the reaction must proceed in time (ie 8 hours in Example 1) to a predetermined relative endpoint. Furthermore, the end point is tracked and the concentration of reducing sugars is measured and defined. 1.4-α-
Maltose produced by D-glucosidase activity is a reducing sugar and is quantified by known methods. Other techniques, such as tracking changes in viscosity or changes in molecular weight, are used to define the reaction end point.

In a preferred embodiment, the endpoint of decomposition is determined by determining the percentage of reducing sugars contained in the reaction medium. Each maltose unit contains two glucose units, but only one reduced W, which can be detected by the reducing sugar assay. The weight % of reducing sugars (calculated as glucose) is therefore approximately equal to 1/2 of the weight % of maltose units formed by the decomposition of starch molecules. When β-amylase is contaminated with high levels of α-amylase, the reaction medium contains even higher levels of reducing groups, and reducing sugar measurements take into account the effects of such contamination in measuring the progress of enzymatic reactions. It must be standardized. Alternatively, maltose may be measured directly by other types of known analytical methods.

The degree of starch degradation required to substantially improve the low temperature stability of starch compositions is amenable to variation. It is based on the type of starch used, the presence and nature of any substituents and the degree of chemical modification, if any.

It is known that starch degradation varying from 13-55% by weight results in improved low temperature stability in thickeners (
(See U.S. Pat. No. 3,525,672). For low viscosity emulsification applications (i.e. starch modified to -F2O-60), up to 70% by weight of starch (as measured by the reducing sugar content of the starch dispersion) is hydrolyzed to full 1--s continue.

The maximum amount of enzymatic degradation to maltose that can be theoretically achieved using pure β-amylase and modified starch is about 55% by weight to starch. Pure β-amylase is not readily available on the market. Commercially available β-amylases contain small amounts of α-amylase, and in vitro enzymes that randomly cleave internal starch branches separate these branches of β-amylase activity. Starch modification by acid, heat or oxidation has an M-like effect, but β-amylase degradation of starch has no significant effect.

Degradation of starch to 0% by weight can therefore be achieved using commercially available β-amylase contaminated with small amounts of α-amylase.

After the desired degree of starch degradation is obtained, the enzyme is inactivated. It is convenient to rapidly inactivate the β-amylase at a temperature of about 100°C and therefore terminate the reaction by raising the temperature of the starch dispersion to at least 75°C for at least 15 minutes.

It is recognized that the order of steps in the method of the invention can be performed in any order and is not limited to the preferred embodiments described above. Therefore, in a second preferred embodiment, the order is reversed and the enzymatic degradation is completed before the derivatization step.

If the end-use application requires purification of the starch composition,
Maltose and other reaction impurities and by-products can be removed by dialysis, filtration, centrifugation or any other method known for isolation and concentration of starch compositions.

If a dry starch composition is desired for end use application, the starch composition is dehydrated by any known method.

Horsetail corn starch modified to a water fluidity of about 4060 is preferred in beverage flavor emulsions.

For low viscosity emulsifiers, the viscosity reduction during the enzymatic reaction is used to determine when the desired level of degradation is achieved. A method for monitoring the viscosity of a reaction solution is described in Example 1. Any of the many known methods for measuring viscosity can be used. However, viscosity will vary depending on factors other than the desired enzyme activity. For example, if the β-amylase contains large amounts of α-amylase, the decrease in viscosity cannot be directly related to β-amylase activity.

Therefore, carefully track the level of α-amylase contamination and
Adjustments must be made if viscosity changes are used to determine the level of enzymatic degradation.

If the β-amylase or any other 1,4-α-D-glucosidase used according to the invention contains high levels of α-amylase contaminants, the β-amylase should be purified or α-amylase inhibited before use. agents can be added to the reaction dispersion.

The following examples illustrate embodiments of the invention. All parts and percentages in this example are stated per dry weight;
All temperatures are in degrees Celsius unless otherwise specified. Storage stability is measured by accelerating aging at low temperatures and shortening the test period.

Example I This example demonstrates the production of a modified starch of the invention for use in beverage flavor emulsification.

U.S. Patent No. 2,661,349 except that the octenyl succinate derivative of waxy corn starch (O5A) and the corn starch were replaced with waxy corn.
The reaction is carried out by the method disclosed in Example 2 of the specification. O5
A 28% aqueous slurry of Tsukushii corn is added to about 14
Jetcooked at 9°C (300°F)
)do. The heat-treated OSA waxy corn is then placed in a constant temperature bath and kept at 55-60°C with constant stirring. Adjust the pH to 5.3 with 3% hydrochloric acid.

The heat-treated OSA waxy corn dispersion was divided into four batches and treated with varying levels of barley β-amylase (
1,4-α-D-glucan maltohydrolase (E, C
, 3, 2, 1, 2) , Fermukov Iochemics,
Inc., Elk Grove Village, IL. ) to each batch. The amount of enzyme added is 100g of dried OSA waxy corn.
168.334.840 and 1.1100P per ”
It is. It is determined in preliminary tests that this relative range of enzyme concentrations results in the desired starch degradation in about 8 hours. Three batches containing at least 3340 P'/100 g of starch achieve the desired degree of degradation in 3-8 hours.

The degree of degradation is determined by monitoring the final viscosity of the dispersion. Therefore, the amount of α-amylose contamination present in the barley β-amylose is tracked and limited to an enzyme solution of only 0.4 DU/−, but the viscosity is not affected by this change. DU (
Dextrinization unit) is the amount of α-amylase that dextrinates soluble starch at a rate of Igm/h at 20”C in the presence of excess β-amylase.

To measure funnel viscosity, 38 g of modified starch (anhydrous basis) is weighed in a tared 250 d beaker (stainless steel) equipped with a thermometer and distilled water is added to make a total weight of 200 g. Mix the sample to dissolve any lumps and heat or cool to 22°C (72°F). Total 1 tio of heat treated starch dispersion.

-Put into a measuring cylinder and measure. Next, pour into a graduated funnel while covering the hole with your finger. Pour a small amount into a metric glass to remove all trapped air and pour all the remainder remaining in the metric glass back into the funnel. Sample 100d flows through the top of the funnel using a timer.
Record the time required.

The funnel is a standard 58°, thick-walled, durable glass funnel.

The diameter of its apex is 910 cm+, and the inner diameter of the body is approximately 0.
It is 381cm. Add 100 d of water to the funnel through the above treatment.
Mark it so that it passes in 6 seconds.

Carefully adjust the funnel viscosity test parameters and
By limiting α-amylase contamination, the degree of starch degradation by β-amylase is related to viscosity loss. Measure reducing sugar by Fehling's method to confirm the degree of decomposition.

In this example, the desired enzymatic reaction end point is obtained within the funnel viscosity range of 9-50 seconds. The reducing sugar content in this example is 29
-35%. The corresponding breakdown of starch is 58-70% by weight. When the desired viscosity is obtained, the enzyme is inactivated by injecting fresh steam into the reaction solution until a temperature of at least 75° C. is achieved and maintained for at least 15 minutes. The batch is then spray dried using a Standard 221'/4 J nozzle available from Spraying Systems, Inc. at an inlet temperature of 200-210°C and an outlet temperature of 85-90°C. 1 of the spray-dried starch product
Sieve through a 40 mesh sieve.

Example ■ This example illustrates that the aqueous dispersion of the product prepared in Example ■ is stable for multiple freeze/thaw cycles, in other words stable for longer storage. Furthermore, this example illustrates the stability compared to the non-β-amylase degraded control starch of the present invention.

OSA waxy corn and acid-cleaved 50WF OSA waxy corn are degraded with β-amylase using the method described in Example I. β-
In one set of tests, the amylase-digested starch was dispersed in water at 20% solids and placed in a freezer, and the dispersion was subjected to six freeze/thaw cycles, where the freeze portion of the cycle was over a period of 22 days. 1 to 5 days. In another set of tests, the dispersion is subjected to a series of 6 freeze/thaw cycles. In this case, the freezing portion of the cycle is days 1 to 5 of the 18 day period. After each freeze/thaw cycle,
The viscosity was measured at room temperature (approximately 22°C) using a Bookfield viscometer.
(72°F)) on a #3 spindle at 10 rpms.

The viscosity of the control increases and visible flocs
) is formed and then the viscosity decreases. The viscosity of the enzyme-treated sample is low and shows almost no change other than the inherent change in the Hookfield viscometer reading. Furthermore, the flocs formed in the control after one freeze/thaw cycle are absent in the enzyme-treated samples even after six freeze/thaw cycles. Thus, enzymatically degraded starch compositions exhibit greater retrogradation resistance during temperature changes, ie during shelf storage, compared to control compositions currently used in place of gum arabic in beverages.

Example ■ This example illustrates that modified starch purified by removal of liberated maltose with β-amylase still maintains resistance to retrogradation during storage.

The β-amylase-degraded O5A waxy corn produced by the method described in Example 2 above is dialyzed to remove maltose. Starch in distilled water 15-20
% solids and placed in dialysis tubing (obtained from Spectropor membranes) maintaining molecules with an excess molecular weight of 6,000-8,000.

The dispersion is dialyzed against distilled water until the dialysate is free of all organic material. The starch is then precipitated with ethanol and collected.

example! In addition to maltose-containing samples prepared similarly as in , maltose-poor samples are cooled at 5-7° C. for 83 days. Samples were removed periodically and subjected to differential scanning calorimetry (DS).
C) Determine the minimum number of days required for the sample to age upon analysis. DSC analysis is A.

A method reported by C. Eliasson, “Aging of Starch Determined by Differential Scanning Calorimetry” Prog, Biotechnol,
1:93-8 (1985).

The maltose-free sample shows no aging even after 83 days of storage under refrigeration. Thus, like the maltose-containing β-amylase degraded starch, the maltose-free starch exhibits increased retrogradation resistance compared to the currently used O3^ waxy corn emulsifier. (See Table I). Therefore the presence of maltose is not essential to improve the stability of degraded starch.

Steal--L β-amylase decomposition OSA derivative of starch maize β-amylase decomposition OSA derivative of oxidatively modified waxy maize β-amylase decomposition of oxidatively modified waxy maize Myristate ester derivative Maltose of waxy maize Non-containing β-amylase-degraded O3A derivative control: Waxy corn O5A derivative control: α-Amylase-modified waxy corn OSA derivative control: Oxidation-modified waxy corn DSC-based 50% starch dispersion control O3A derivative control for 83 days or more, 83 days or more, 83 days or more, 4 days, 14 days: Example of 4 days of oxidized Tsukushii maize ■ This example shows that the starch degraded by β-amylase is improved during storage. Explain that it exhibits excellent aging resistance.

A 50% solids aqueous dispersion is prepared using the following starches: 1) β-amylase degraded OSA waxy corn (
The above example ■), 2) β-amylase decomposition and 50-F oxidized waxy corn (the above example ■), 3) β-amylase decomposition produced by the following method,
50-row oxidation-modified waxy corn myristate ester; 4) 50-row oxidation-modified waxy corn control myristate ester; 5) α-amylase-modified OSA wax. 6) Oxidized O3^ Waxy Corn Control, and 7) O5A Waxy Corn Control.

All β-amylase degraded samples are prepared as described in Example I. All OSA samples are prepared as described in Example I. Add the Myristate ester sample to 30% water.
Slurry 200 g of 50-F oxidized waxy corn in 0 wd, adjust the pH to 8.0 by adding 3% NaOH, and add 20 g of N-myristyryl-N-methylimidazolium chloride for 10-15 min. Manufactured by pouring and adding. The reaction is continued for 2 hours and more water is added to allow stirring when the reaction mixture becomes viscous. The reaction mixture is filtered, the starch is resuspended and the pH is adjusted to 5.5, then filtered, washed with methanol and dried. The starch product contains about 5% by weight myristate esters.

In addition to the control and the maltose-free sample of Example 1 above, this starch dispersion is stored under cooling at 5-7°C. Periodically, the samples are evaluated for aging by the OSC analysis method described in Example 3.

Table I shows the points that can be detected by DSC analysis.
The number of days required for each starch composition to age is summarized.

The results show that the control, which was not treated with β-amylase, aged rapidly, while the treated samples did not age to the point detectable by DSC analysis during the 83 days that the test was being conducted.

Example V This example illustrates that various starches and starch derivatives exhibit improved storage stability and, in some cases, improved emulsion-forming ability after β-amylase degradation.

19 parts solid and viscosity through the funnel at 22°C (72°F) 33
．． A group of starches including oxidized modified tapioca having 6s, 40 WF fluidity corn and hydroxypropyl 80 WF oxidized waxy corn derivatives were reacted with octenylsuccinic anhydride in the manner described in Example I to form OSA derivatives. Eggplant. A 5% myristate ester derivative of 50-F waxy corn is prepared as described in Example 2.

A mixture of C14-Cz4 hydrocarbon chain ethers of waxy corn starch was mixed with 100 g of starch and 3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride (Quab 360CC1b).
-taHzs-xz N0Ch), obtained from Degussa. ) at pH 11.5-12. The starch mixture was heated to 40 °C and reacted for 16 hours, then neutralized to pH 5,5-6, washed with water three times,
dry.

This starch ester derivative was prepared using the method described in Example I.
Subjected to amylase digestion and (with one exception) then spray dried. The exception is that the β-amylase degradation is terminated when the funnel viscosity of the reaction medium reaches that of a control mixture of Cr b-Cta hydrocarbon chain ether of waxy corn starch. A control starch ether is prepared by the method described above, in which the starting compound is oxidatively modified 50% waxy corn starch.

All other samples of the respective starch derivatives are subjected to enzymatic digestion in the manner described in Example 2 and then spray dried.

A sample of the spray-dried starch derivative (20 g) is mixed with 180 g of distilled water. The dispersion is stirred in a Waring Brengu for 2 minutes at low speed using a powerstat set at 25-30. Citrus oil mixture (
80 g) at slow speed into the center of the vortex. Citrus oil mixture
single fold orange oil obtained from tzsche-Dodge-01cott)
2 parts and 3.4 parts of Ester Gum #8 BE obtained from Hercules. Emulsify the starch dispersion and oil in a Waring Breguer at high speed for 2 minutes. The resulting emulsion is placed in a glass jar, capped, and placed in the freezer, which is removed periodically to warm to room temperature. The evaluation consists of visually examining the emulsification via separation, oiling and gelling. All samples, except those that do not form emulsions stable at room temperature, are also evaluated after cooled storage.

The control 40WF oxidized O5A corn stirrer gels at room temperature and does not form an emulsion. Control hydroxypropyl 84WF oxidized waxy corn and control myristate esters of 50WF oxidized waxy corn form emulsions that separate readily at room temperature. Similarly, the control oxidized tapioca does not form an emulsion. The 5° oxidized waxy corn control ether forms a poor emulsion.

It appears as a pale yellow cream at room temperature and becomes oily after cooling for 1 day.

In contrast, β-amylase degraded 4° WF oxidized modified OSA corn starch forms an emulsion that separates only after two freeze/thaw cycles, and β-amylase degraded 4° WF oxidized modified OSA tapioca starch forms an emulsion that separates only after two freeze/thaw cycles. An emulsion is formed that is separated after multiple freeze/thaw cycles. β-amylase degraded hydroxypropyl-0SA is stable for 7 freeze/thaw cycles. Waxy corn β-amylase-degraded 5
% myristate ester forms an emulsion that is stable during one freeze/thaw cycle and after three weeks of refrigerated storage. The waxy corn β-amylase-cleaved ether is stable at room temperature and forms an emulsion that remains stable after two freeze/thaw cycles over 12 days. All other β-amylase treated samples form emulsions that are stable after 6 months of cold storage. In all cases, the β-amylase degraded samples perform better than their respective controls.

The results show that β-amylase degradation of OSA starches, such as waxy maize, corn and tapioca derivatives, improves the storage stability of oil-in-water emulsions formed with these starches. The results obtained are also the same whether the starch is derivatized with hydrophobic/hydrophilic substituents, such as OSA, or only with hydrophobic substituents, such as myristate. The results further show that where specific applications require derivatives such as hydroxypropyl O34 waxy corn, enzymatic degradation of such derivatives yields low temperature stable oil-in-water emulsions.

Example ■ This example illustrates that the modified starch of the present invention is as resistant to storage aging as gum arabic, and more resistant than starch-based emulsifiers currently used to emulsify flavor oils in beverages. do.

Waxy corn and 50-F oxidized O5
Example I of enzymatically decomposed O5A derivatives of waxy maize A.
Manufactured by the method described in . This starch composition and the control, which contains gum arabic and oxidized OSA waxy corn currently used in beverage flavor oils, are emulsified in the manner described in Example 1.

These emulsions are stored refrigerated for 3 months.

Bookfield viscosity is measured at the beginning and then after 3 months. The measurement uses a 115 spindle with a viscosity of 1000-
The method described in Example 3 is used except that it is used for 5000 cps. Good emulsion stability is observed when the enzymatically degraded sample is visually observed after 3 months of cooling. The viscosity measurements are summarized in Table ■.

Feces-1 IL decoy ■ Viscosity change in flavor oil emulsion after 3 months of cold storage riLML3 'r' 0) CPS (cps) Oxidized waxy maize β-amylose-degradation OSA derivative waxy maize β-amylose-degraded OSA derivative of waxy maize β-amylose-degraded O5A derivative control of oxidized cotton corn O5A derivative control: Gum arabic! 36 The results show that emulsions made from β-amylase degraded starch compositions are as resistant to viscosity change, gelling and oiling during storage as gum arabic emulsions.

In aqueous dispersions and emulsions, the modified starches according to the invention exhibit improved aging resistance and a stability that is improved over the storage stability of currently known starch emulsifiers.

EXAMPLE ■ This example shows that the modified starch of the invention can be made by reversing the order of the steps described in Example I.

A 28% solids aqueous slurry of waxy corn starch was prepared, the pH was adjusted to 6.0-6.3 by the addition of 3% NaOH, and the slurry was heated to about 149°C (300°F).
) for injection heat treatment. The heat-treated starch is placed in a constant temperature water bath and kept at 55-60°C with constant stirring. The barley β-amylase used in Example ■ was added to heat-treated starch at a concentration of 1 per 100 g of dry weight of starch.
．． The batch of β-amylase used in this example has an α-amylase activity of 0.9 DU/-
has. The degree of decomposition is followed by the through-funnel viscosity procedure described in Example ■.

When the starch reaches a 30 second funnel viscosity, add 1 of the enzyme.
The pH is reduced to 3.5-4.0 to inactivate by addition of 0% HCI and the starch is kept at this pH for 30-60 minutes.

After inactivation, the pH is adjusted to 7.0 with the addition of 3% NaOH.

The OSA derivative is prepared by intimate mixing of 3 g of octenylsuccinic anhydride per 100 g of dry weight of starch with the neutralized debranched starch dispersion. The reaction can be continued for 4 hours at room temperature with good stirring.

A portion of this starch dispersion is spray dried in the manner described in Example I.

An orange oil emulsion was prepared from a commercially available control starch (an oxidized modified O3A waxy corn derivative) and a debranched starch spray-dried aqueous dispersion for use as an emulsifier as in Example 3. Produced from a liquid sample. subjecting the emulsion to at least 8 freeze/thaw cycles for 1 to IO days;
Evaluate as in Example ■.

The control starch forms an emulsion with a thick orange oil film covering the water surface after one freeze/thaw cycle. In contrast, debranched starches form emulsions that are stable for at least five freeze/thaw cycles. The spray dried starch sample is stable for 6 cycles. The aqueous starch dispersion sample exhibits a thin orange oil film on the water surface at the beginning of the 6th cycle.

Emulsions using the modified starches of the invention, which are produced by enzymatic degradation of starch either before or after the production of starch derivatives, have improved retrogradation resistance and use one of the commercially available starch emulsifiers. Shows improved stability over storage stability of emulsions.

Claims (1)

[Scope of Claims] 1) Consisting of a starch derivative containing a hydrophobic group or a hydrophilic group and a hydrophobic group, up to 70% by weight of which contains 1,4-α-D-glucoside bonds from the non-reducing end of starch. Improved stability, oiliness and gelation resistance during storage, degraded by in vitro enzymes that can cleave but not the 1,6-α-D-glucoside bonds of starch A modified starch that has the emulsifying properties of an emulsion. 2) The starch is acid- or heat-modified or converted to a water fluidity (WF) of up to about 60 by α-amylase, the in vitro enzyme is β-amylase, and the starch is gelatinized waxy corn starch. , the starch contains at least 0.0% octylsuccinic anhydride per dry weight of starch.
Modified starch according to claim 1, which is derived by treatment with 25%. 3) The hydrophobic group consists of an alkyl-alkenyl-, aralkyl-, or aralkenyl group having at least 5 C-atoms, and starch derivatives with hydrophobic and hydrophilic groups have the following formula starch ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R is a group selected from the group of dimethylene and trimethylene groups, R' is an alkyl group having at least 5 C atoms)
, alkenyl-, aralkyl or aralkenyl group, and the carboxyl group COOH is a hydrophilic group. ) The modified starch derivative according to claim 1, comprising a substituent group. 4) Next step: a) producing a gelatinized starch derivative;
The derivatives are characterized by a hydrophobic group or a respective substituent containing a hydrophilic group and a hydrophobic group; b) up to 70% by weight of the starch derivative from the non-reducing end of the starch to the 1,4-α-D-glucoside; improved stability during storage, consisting of degradation to maltose with an in vitro enzyme capable of cleaving the bonds, but not of the 1,6-α-D-glucoside bonds of starch; A method for producing a modified starch having emulsifying properties of an emulsion exhibiting oiliness resistance and gelation resistance. 5) The starch is waxy corn starch;
This is acid- or thermo-modified or modified to a WF of up to about 60 prior to in vitro enzymatic treatment with α-amylose and the starch is treated with at least 0.25% octenylsuccinic anhydride per dry weight of starch. 5. The method according to claim 4, wherein the method comprises: 6) The in vitro enzyme is β-amylose, which undergoes enzymatic degradation with a diastase power of 334-1110 per 100 g of starch per dry weight in an aqueous dispersion containing up to 33% solids.
with a pH-range of 3-10 and 20-75
5. A method according to claim 4, which is carried out at a temperature range of .degree. 7) The hydrophobic group of the starch derivative consists of an alkyl-, alkenyl-, aralkyl- or aralkenyl group having at least 5 C atoms, and the starch derivative containing a hydrophilic group and a hydrophobic group has the following formula starch ▲ mathematical formula, chemical formula , tables, etc. ▼ (wherein R is a group selected from the group of dimethylene and trimethylene groups, R' is an alkyl group having at least 5 C atoms.
, a hydrophobic group consisting of an alkenyl-, aralkyl- or aralkenyl group, and a carboxyl group COOH are hydrophilic groups. ) The method according to claim 4, wherein the substituent is: 8) Next steps: a) Up to 70% by weight of gelatinized starch can be cleaved from the 1,4-α-D-glucosidic bond from the non-reducing end of the starch, but the 1,6-α- decompose it to maltose with an in vitro enzyme that cannot cleave the D-glucoside bond; b) an agent that produces a starch derivative containing enzymatically decomposed starch and a hydrophobic group or a hydrophilic group and a hydrophobic group; A method for producing a modified starch having emulsifying properties of an emulsion exhibiting improved stability, oiling resistance and gelation resistance during storage, comprising reacting. 9) An industrial or food emulsion containing the modified starch according to claim 1. 10) An industrial or food emulsion containing the modified starch produced according to claim 4 or 8.