EP4308612A1

EP4308612A1 - Use of waxy wheat starch as a viscosity enhancer

Info

Publication number: EP4308612A1
Application number: EP22712423.7A
Authority: EP
Inventors: Dietmar Grüll; Helene PERSAK; Robert Wittenberger
Original assignee: Suedzucker AG
Current assignee: Suedzucker AG
Priority date: 2021-03-17
Filing date: 2022-03-16
Publication date: 2024-01-24
Also published as: WO2022194907A1; EP4059965A1

Abstract

The invention relates to uses of waxy wheat starch as a viscosity enhancer in a liquid or viscous composition, the viscosity-enhanced composition exhibiting a substantially constant progression of the storage modulus (G') over a period of six weeks.

Description

Use of waxy wheat starch as a viscosity improver

The raw material starch is obtained from plant products, mainly cereals and potatoes, although other plant products are also used industrially in subtropical regions to produce starch. Starches are commonly found as tuber, corn or legume starches, e.g., pea starch, corn starch, potato starch, amaranth starch, rice starch, wheat starch, barley starch, tapioca starch and sago starch. Starches of natural origin usually have an amylose content of 20 to 30% by weight, depending on the plant species from which they are obtained.

Chemically, starch is a mixture of two structurally different polyglucans, namely amylose and amylopectin, both of which consist of a large number of linked glucose molecules. Amylose is characterized by an almost unbranched linear structure of linked glucose units. In amylopectin, numerous shorter molecules with an amylose-like structure are bound to form a larger, branched structure.

The usual natural starches contain about 15% to 30% amylose, depending on the plant species from which they are obtained. Special plant genotypes obtained by crossing or targeted genetic manipulation can also contain other proportions of the two starch molecules. So-called high amylose starches with an amylose content of up to 70% are known, as are so-called amylopectin starches, which contain up to 98% amylopectin. Such an amylopectin starch is, for example, waxy corn starch, which is obtained from a corn genotype in which the starch produced is almost free of amylose. The term "waxy" comes from the fact that the corn kernel has a waxy appearance.

Plant genotypes of this type are also known for wheat, from which almost amylose-free starch, also known as waxy wheat starch, can be obtained.

WO 2019/133836 A1 discloses baked goods with improved properties that contain pregelatinized waxy cassava starch, optionally mixed with other starch components such as waxy starches based on wheat, rice, potatoes, corn, oats, sago, arrowroot, peas, beans, lentils and other legumes . The baked goods contain between 1% and 10% by weight waxy cassava starch and have the same or better crumb resistance than baked goods using chemically modified starches.

WO 2019/089656 A1 describes a starch mixture containing 40-85% (w/w) of an unmodified, amylose-containing starch and 15-60% (w/w) of a non-chemically inhibited starch. When boiled in water, the starch mixture has a high viscosity even after several freeze-thaw cycles. Such a starch blend is disclosed to be useful in a variety of food and beverage compositions, particularly frozen sauces and sauces. The starch may be any variety including, for example, corn, potato, sweet potato, barley, wheat, rice, sago, amaranth, tapioca (cassava), arrowroot, canna, pea, lentil, fava (field), banana, oat, rye, Triticale or sorghum, where the non-chemically inhibited starch can also be low-amylose (waxy) varieties of such starches.

WO 2019/055381 A1 discloses thermally inhibited waxy cassava starches and edible compositions made therefrom. Such compositions may contain other standard edible ingredients, such as other starches and/or flours from any source (e.g., wheat, corn, rice, potato, legume, arrowroot, sorghum, sago, etc., and waxy or high amylose variants thereof).

WO 2019/005861 A1 is directed to pregelatinized starches and methods for their production and use, the pregelatinized starches being selected from tapioca or manioc starch, potato starch, rice starch or wheat starch, starches from acorns, arrowroot, arracacha, bananas, barley, breadfruit, Buckwheat, canna, colacasia, katakuri, kudzu, malanga, millet, oats, oca, Polynesian arrowroot, sago, sorghum, sweet potato, rye, taro, chestnuts, water chestnuts, yams, or beans such as B. favas, lentils, mung beans, peas, or chickpeas , the starches can be waxy or non-waxy.

WO 2018/112383 A1 and US 2019/0380370 A1 relate to inhibited waxy starches based on corn, wheat or tapioca with an amylopectin content in the range of 90-100% and a sedimentation volume in the range of 10-50 m/g, the amylopectin fraction of inhibited waxy starch has no more than 48.5% medium-length branches with a chain length of 13-24 and the starch is not pregelatinized. Such starches can exhibit a non-cohesive, smooth texture upon gelatinization and are tolerant of processing conditions (such as heat, shear, and/or extremes of pH), and exhibit rheological and structural stability for a desired shelf life, including under refrigeration and/or or freeze/thaw conditions.

WO 2014/042537 A1 discloses a process for producing thermally inhibited starch, which leads to a viscostable starch product. The method starts from an alkaline starch with a pH, measured in a 20% (w/v) aqueous dispersion, of between 9.1 and 11.2, with the water content of the starch being adjusted to between 2 and 22% by weight, followed by heating the starch between 130 and 190°C, in particular between 140 and 180°C, for thermal inhibition of the starch. The starch to be used may be any common type of starch including corn, potato, tapioca, rice, wheat etc. and may contain at least, for example 70% (w/w) amylopectin.

WO 03/075681 A1 describes chemically crosslinked and/or substituted waxy wheat starch which is stable to acidic conditions between pH 3 and a pH of less than 7, is freeze and thaw stable and food products containing such wheat starch which have a smooth and have a creamy mouthfeel. WO 02/096220 A1 describes partially waxy wheat flour with an amylose content of 10% by weight to 20% by weight and baked goods made from a flour or a flour mixture containing such a wheat flour.

US 2018/0263268 A1 is directed to a coated snack made using two starch components, one of which is a spray-cooked agglomerated waxy corn starch having a specified peak time to hydration viscosity. Also disclosed is the use of waxy wheat starch in place of the waxy corn starch.

US 2015/0239994 A1 provides a process for the production of an inhibited starch and the use of the inhibited starch for the production of a food product, the process comprising treating the partially refined starch with a bleaching agent to provide an inhibited starch. The source of the starch is selected from the group consisting of waxy maize (corn), waxy rice, waxy wheat, waxy sorghum, waxy barley and waxy potato. Foods that can be improved through the use of the inhibited starches include high-acid foods (pH <3.7) such as fruit-based pie fillings, baby foods, and the like; acidic foods (pH 3.7-4.5) such as tomato-based products; and low-acid foods (pH> 4.5) such as sofien, sauces and soups.

US 2007/0122536 A1 discloses methods for producing food products comprising wheat and/or rye flour and added fat, wherein the flour is replaced by 0.5 to 100% by weight of waxy wheat flour to reduce the fat content in the food product.

US 2003/0138541 A1 relates to dough compositions comprising from about 50% to about 70% of a starch-based material and potato flanules, and food products made therefrom. The starch-based material includes corn starch, wheat starch, rice starch, waxy maize starch, oat starch, cassaya starch, waxy barley, waxy rice starch, glutinous rice starch, sweet rice starch, amioca, potato starch, tapioca starch, and mixtures thereof and may be physically or chemically modified.

US 2003/0008049 A1 provides a storage-stable, buoyant wax granule, wherein the wax granule can be waxy triticale and waxy wheat. The starch in the wax granule is fully gelatinized and the cooked wax granules can be stored in airtight or conventional grain containers for long periods of time. A 25 second roasting of the dried product at 204°C is described.

US 2002/0037352 A1 is directed to a whole grain waxy wheat flour or starch and also describes a method for producing such a wheat flour, including the production of a starting flour with a defined size classification starting from whole grain waxy wheat grains and a heat-moisture treatment including gelatinization of the starch between about 15 and about 99% in less than about 5 minutes. The use of such a waxy wheat flour or starch in various foods is also disclosed. EP 2 866 581 B1 relates to a process for producing thermally inhibited starch by thermal treatment in a helical vibrating conveyor, the starch can come from wheat with a low amylose content, for example.

CN 104759309 A discloses a production process for waxy wheat powder, comprising repeating moistening and wetting treatment of the waxy wheat at a temperature of not higher than 20 to 30°C.

Hu Xia-Pei et al. (Food Chemistry, Elsevier, Vol. 157, 2014, pp. 373-379) investigates effects of single, dual and triple retrogradation on the in vitro digestibility and structural properties of waxy wheat starch.

Zhang Bo et al. (LWT - Food Science and Technology, Academic Press, UK; Vol. 136, 2020) relates to the physical modification of waxy wheat starch by means of thermal treatment. The influence of continuous and repeated thermal treatment on physical properties was investigated.

WO 2020/086916 A1 relates to a processing method for producing a physically modified starch, in which the pH of an aqueous starch mixture is adjusted to at least about 8. For physical modification, the starch is treated at 100-190 °C for approx. 15-240 minutes. The use of physically modified starches in the food sector is also disclosed.

Surprisingly, it has now been found that a waxy wheat starch, in particular a physically and/or chemically modified waxy wheat starch, has outstanding properties as a viscosity improver both in the food and non-food sectors, which make its use appear favorable in the respective area. Especially in the food sector, this use as a viscosity improver is accompanied by improved stabilization of the food in question; it is particularly favorable if the food has a pH in the acidic range.

It was also surprisingly found that a chemically modified waxy wheat starch has increased acid stability compared to a similarly chemically modified waxy maize starch, which means that the use of such a chemically modified waxy wheat starch appears favorable in all those areas where increased acid stability is desired.

Thus, according to the invention, the use of waxy wheat starch as a viscosity improver in a liquid or viscous composition is provided, with the composition showing a substantially uniform course of the storage modulus G' over a period of 6 weeks. The storage modulus, together with the loss modulus, is part of the complex shear modulus. In general, the complex shear modulus has the form of a complex number:

G * = G ' + i G " {\displaystyle G ^A {*}=G'+i\cdot G"} G* = G ^' + iG with the storage modulus G ' {\displaystyle G ¹ } G ^' (real part), which stands for the elastic part (proportional to the part of the deformation energy that is stored in the material and can be recovered from the material after unloading) and the loss modulus G " (\displaystyle G") G“ (imaginary part), which stands for the viscous part (it corresponds to the loss part of the energy, which is converted into heat by internal friction). In the course of the present invention, “substantially uniform” is understood to mean a deviation of the individual measurements of the storage modulus G ^′ from the mean of less than 10% over 5 weeks.

The waxy wheat starch used according to the invention can also be a modified or functionalized waxy wheat starch, if the term "waxy wheat starch" is used in the present description and in the claims, this also means a functionalized waxy wheat starch. Functionalization includes, for example, etherifications or esterifications. Some derivatizations are described below, which can be provided alone or in combination with one another for further derivatization of the waxy wheat starch derivatives. The type of derivatization and the raw material basis of the waxy wheat starch used are very closely related to the specific area of application of the respective product. The methods for this are known per se, in particular the focus here should be on functionalization in the slurry, in the paste, (semi)dry processes and functionalization by means of reactive extrusion.

In general, starch derivatives are divided into starch ethers and starch esters. Furthermore, a distinction can be made between non-ionic, anionic, cationic and amphoteric as well as hydrophobic starch derivatives, which can be produced via slurry, paste, semi-dry or dry derivatization as well as via derivatization in organic solvents.

Anionic and nonionic functionalization of starch summarizes those derivatives in which the free hydroxyl groups of starch are substituted by anionic or nonionic groups. Starch can also be anionically functionalized by oxidative processes such as, for example, the treatment of starch with hydrogen peroxide or hypolyte or by a laccase/mediator system.

In principle, the anionic and nonionic derivatization can be carried out in two ways: a) The starch is esterified by the functionalization. Inorganic or organic acids or salts thereof, or esters thereof, or anhydrides thereof, are used as functionalizing agents. Mixed esters or anhydrides can also be used. When the starch is esterified, this can also take place several times, so that, for example, distarch phosphoric acid esters can be produced. The starch used according to the invention is preferably the result of an esterification with mono-, di- or tricarboxylic acids having an alkyl chain with 1 to 30 carbon atoms or a carbamate, particularly preferably acylated, such as succinylated, octenylsuccinylated, dodecylsuccinylated or acetylated. b) In the course of the functionalization, the starch is etherified. Methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, cyanoethyl, carbamoylethyl ether starch or mixtures thereof can be used.

Cationic functionalization of starches includes those derivatives in which a positive charge is introduced into the starch through substitution. The cationization processes are carried out with amino, imino, ammonium, sulfonium or phosphonium groups. Such cationic derivatives preferably contain nitrogen-containing groups, in particular primary, secondary, tertiary and quaternary amines or sulfonium and phosphonium groups, which are bonded via ether or ester bonds.

Another group are the amphoteric starches. These contain both anionic and cationic groups, which means that their possible uses are very specific.

These are mostly cationic starches that are additionally functionalized either by phosphate groups or by xanthates.

With the esters, a distinction is made between simple starch esters and mixed starch esters, where the substituent(s) of the ester can be of different types: In the ester radical RCOO-, the radical R can be an alkyl, aryl, alkenyl, alkaryl or aralkyl radical having 1 to 20 carbon atoms, preferably 1 to 17 carbon atoms, preferably having 1 to 6 carbon atoms. These products include the derivatives acetate (made from vinyl acetate or acetic anhydride), propionate, butyrate, stearate, phthalate, succinate, oleate, maleate, fumarate and benzoate.

Etherifications are largely carried out by reaction with alkylene oxides (hydroxyalkylation) containing 1 to 20 carbon atoms, preferably 2 to 6 carbon atoms, in particular 2 to 4 carbon atoms, in particular by using ethylene oxide and propylene oxide. However, methyl, carboxymethyl, cyanoethyl and carbamoyl ethers can also be prepared and used. The reaction of starch with monochloroacetic acid or its salts is given as an example of a carboxyalkylation. Also specifically mentioned are hydrophobic etherification reagents, such as glycidyl ether or epoxides. The alkyl chain length of the reagents mentioned is between 1-20 carbon atoms, and aromatic glycidyl ethers are also possible.

Examples of derivatization with glycidyl ethers are o-cresol glycidyl ether, polypropylene diglycol glycidyl ether, tert-butylphenyl glycidyl ether, ethylhexyl glycidyl ether, hexanediol glycidyl ether and neodecanoic acid glycidyl ester.

Another possibility for alkylation is alkylation via alkyl halides, for example via methyl chloride, dialkyl carbonates, e.g. dimethyl carbonate (DMC) or dialkyl sulfate, e.g. dimethyl sulfate.

Processes for the derivatization of starch to produce ethers and esters in general are well known in the art and are described, for example, in OB Wurzburg (Ed.): Modified Starches: Properties and Uses, CRC Press Inc., Boca Raton, Florida, 1986, chap. 4, 5 and 6. The starches used for the esterification, etherification and crosslinking and also the chemically non-functionalized starches can also be tempered (in the slurry) or inhibited (dry or semi-dry reaction) via thermal-physical modifications.

Starches can also be functionalized using hydrophobing agents. Etherified hydrophobic starches are obtained when the hydrophobic reagents contain a halide, an epoxide, a glycidyl, a halohydrin, a carboxylic acid or a quaternary ammonium group as the functional group. For esterified hydrophobic starches, the hydrophobic reagent most often contains an anhydride. The starch can also be made hydrophobic by mixing a starch or a starch derivative with a fatty acid ester.

All of the functionalizations of the starch mentioned are also used for the waxy wheat starch used according to the invention; they can be achieved not only by converting native waxy wheat starch, degraded forms can also be used. The degradation processes can be hydrolytic (acid-catalyzed), oxidative, mechanical, thermal, thermochemical or enzymatic. As a result, the waxy wheat starch can not only be changed structurally, the starch products can also be made cold water soluble or cold water swellable.

For example, it was surprisingly found that a crosslinked waxy wheat starch according to the invention, in particular a phosphate crosslinked waxy wheat starch, exhibits lower syneresis when determining the freeze/thaw stability than a comparable crosslinked waxy maize starch. This is advantageous for use in the food sector, since the stability and consistency of the product are retained over longer storage periods. This also prevents water from escaping from frozen products after thawing.

It was also surprising that when waxy wheat starch was enzymatically degraded, the use of less enzyme compared to wheat starch was sufficient to set a defined paste or glue viscosity and at the same time to achieve greater stability of the paste obtained, which is particularly beneficial when used in the paper sector .

Finally, the waxy wheat starch used according to the invention can also be present as a graft polymer or as a graft copolymer, such as with products from the group of polyvinyl alcohols or polyesters.

Preferably, the waxy wheat starch used in the present invention is a physically modified waxy wheat starch.

A preferred embodiment of the present invention provides for the use of waxy wheat starch in a liquid or viscous composition with a viscosity of more than 10,000 mPa.s at 20° C., the composition having a pH in the acidic range. According to the invention, the use of waxy wheat starch in liquid or viscous foods is particularly preferred.

It is favorable here if the pH of the composition is between 3.0 and 6.5.

According to a preferred embodiment of the present invention, the use of physically modified waxy wheat starch is provided, wherein the waxy wheat starch has been physically modified at a product temperature between 150 and 200°C, preferably between 165 and 190°C and particularly preferably between 175 and 180°C.

According to a further embodiment of the present invention, the use of physically modified waxy wheat starch is provided, wherein the waxy wheat starch is physically modified during a treatment time of 15 to 120 minutes, preferably during a treatment time of 30 to 105 minutes and more preferably during a treatment time of 60 to 90 minutes became.

It is also favorable if, when using physically modified waxy wheat starch, it has been physically modified in a spiral vibrating conveyor. The use of a helical vibrating conveyor allows not only a continuous physical modification of the waxy wheat starch, but also a stable temperature control, so that a high level of reproducibility and homogeneity of the modified waxy wheat starch according to the invention can be guaranteed. Because of the good homogeneity, the modified waxy wheat starch according to the invention is very well suited for use in compositions with an acidic pH and a viscosity of over 10,000 mPa.s (at 20° C.), since surprisingly good long-term stability is ensured.

According to another preferred embodiment of the present invention, when physically modified waxy wheat starch is used, it is physically modified in a fluidized bed oven.

When using physically modified waxy wheat starch to improve the viscosity of food, it is preferably selected from mayonnaise, confectionery cream and fruit preparations.

Enzymatically degraded wheat starches have long been used in the paper industry for surface sizing of paper. The starch is enzymatically broken down at a concentration of around 20-25% and then applied to the paper surface as a diluted starch paste, with the aim of increasing the strength of the paper.

Starch products are also used as co-binders in paper coatings, typically heavily degraded dextrins, some of which are also added dry to the coating. The low dry substance of the paste, which negatively influences the solids content of the coating colors, speaks against the use of enzymatically degraded starches as an alternative to dextrins in coating colors for paper coating. If the dry substance of the paste is increased, the starch must also be broken down significantly more in order to to set a workable viscosity of the paste, which leads to a loss of cohesiveness, since the cohesiveness of a degraded string depends directly on the degree of degradation. The storage of highly concentrated paste is also problematic and often not possible due to the tendency towards retrogradation.

Surprisingly, it has now been found that when using enzymatically degraded waxy wheat starches in surface sizing or in paper coating colors, the viscosity of the paste is significantly lower and the stability of the paste is significantly better than when using enzymatically degraded wheat starch with a comparable degree of degradation. As a result, highly concentrated, low-viscosity paste can be produced with an optimal degree of degradation, which is particularly suitable for use in the paper industry for the above-mentioned purposes.

Another advantage of using WWS in the paper industry is that due to the lack of amylose, there is no RAPs (Retrograded Amylose Particles) formation, which is particularly the case when using enzymatically degraded starches (e.g. corn and wheat starch) in surface sizing and in the paper coating is very problematic.

examples

The present invention will now be explained in more detail using the following examples, without being restricted.

Test series Ί: Thermal functionalization of alkalized waxy maize starch and waxy wheat starch and LM-AWT investigations

Alkalized waxy wheat starch (WWS) and waxy maize starch (WMS) were processed under the same conditions at 150 °C to 200 °C for 30-120 min in a spiral vibratory conveyor (tube inside diameter 0.2 m, tube length 8.5 m and tube inside volume 0.3 m ³ , Vibration speed 700 rpm, motor angle 20° and drive motor 90%) thermally, ie physically, functionalized and the products comparatively characterized. The native starting materials were previously alkalized to a pH of 8-10 with sodium hydroxide solution, then dried and ground.

alkalization and grinding

30-35% suspension of the respective strengths prepared, pH of the suspension adjusted to 9.5 with 3% sodium hydroxide solution, 30 min stirring at room temperature, centrifugation with the bag centrifuge (Carl Padberg Zentrifugenbau GmbH, laboratory centrifuge, type LS, filter bag 11 miti, material PP), drying in a drying cabinet at 60°C to a water content of approx. 8-12% and grinding of the pre-dried starches with an Alpine mill (Hosokawa Alpine AG, fine impact mill, type UPZ100).

Functionalization in the bowl feeder

All attempts are divided into 3 zones. In the first zone, the alkalized and ground starch is pre-dried at 130 °C. At the end of pre-drying (end of zone 1), the water content is Strength at about 2%. Zones 2 and 3 serve to functionalize the starches (standard temperature 170 °C or 175 °C).

The functionalization period starts when zone 2 is reached. Intermediate samples were taken after a functionalization period of 20 minutes and 40 minutes (corresponds to 20 minutes and 40 minutes in zone 2). At the end of the functionalization (end of zone 3), the hot starch is transferred to a jacketed mixer (20L Lödimischer from AVA, Ploughshare mixer type with vacuum equipment) and mixed there within 20-25 minutes. cooled to room temperature. The cooled starch is the final sample of the respective test and is marked with "cooled" in the sample designation.

Production and testing of food preparations

The functionalized WWS and WMS produced according to F3 - F6 were tested in fruit preparations, vanilla cream and mayonnaise.

Rheological measurements

The measurements served the theological characterization of the samples in food systems. These measurements were made with the Physica MCR-301 rheometer (Anton Paar, AT) according to method AT-L 02 (measuring plate PP50, 25°C, 1mm gap width, amplitude sweep 0.1-1000% logarithmic, frequency f = 1 Hz, frequency sweep: Frequency f = 30-0.1 Hz logarithmic) measured and evaluated in rotation and oscillation. The food preparation was stored in a cool place and measured rheologically after 24 h and 1-6 weeks in order to be able to determine the storage stability. A high storage stability is shown when the rheological parameters such as storage modulus G' (elastic portion), loss modulus G'' (viscous portion) and loss factor (tanδ = G''/G') remain the same. The storage modulus and, in part, the loss modulus are shown in the respective figures as examples of the results. Example 1: Production of 50% mayonnaise

Devices

Stephan universal machine UM/SK 5; Sartorius scales, 2 decimal places

recipe

Components: [%]

A

Strength (in DS) 3.00

water 33.60

Vinegar, 5% 4.00

B

salt 1.20

Granulated sugar 2.00

Tarragon mustard 4.00

Egg yolk powder 2.00

potassium sorbate 0.20

C

Oil 50.00

manufacturing

Components A are weighed, mixed and transferred to the Stephan cooker (smooth blade insert, 10% HM, 60% TF); to 80 °C and after reaching the temperature is kept for 10 minutes, then the paste is cooled down to 25 °C, the components B are added and stirred for 5 minutes under vacuum (50% HM, 60% TF, 200 mbar vacuum ), draw in the oil slowly (about 2 minutes) through the valve in the lid, the mayonnaise is then stirred for another 5 minutes, filled into jars and stored in the refrigerator.

Results of the rheological measurements

It can be clearly seen from Figure 1 that the mayonnaise using the physically modified WMS (lower curve) shows a very even course, while the mayonnaise containing the physically modified WMS (upper curve) shows a significant increase in the storage modulus G' after 4 weeks .

Example 2: Production of confectionery cream 5.5% starch

Devices

Stephan universal machine UM/SK 5; Sartorius scales, 2 decimal places; WiseStir laboratory stirrer HS-100D recipe

Components: [%]

Thickness (in dry matter) 5.50

whole milk 84.43

Aroma (vanilla), liquid, 204960 0.03

Carotene, liquid, A1621 0.04

Granulated sugar 10.00

manufacturing

Weigh and mix all the dry components, weigh and mix all the wet components, stir the cold milk mixture with the propeller mixer and slowly add the dry components until a homogeneous mass is obtained; transfer the mixture to the Stephan cooker (anchor stirrer, HM 10% and TF 60%, vacuum: 200mbar), after applying the vacuum, heat the product to 95 °C and maintain this temperature for 10 minutes, then cool to 30 °C, in Decant jars and store in the fridge.

Results of Theological Measurements

It can be clearly seen from FIG. 2 that the viscosity of the confectionery cream containing the physically modified WMS shows a very uniform course, while the viscosity of the confectionery cream containing the physically modified WMS shows a significant increase in the storage modulus G' after 2 weeks. The phenomenon also shows up in a similar way for the loss modulus, see Figure 3.

Test series 2: Application-related investigations of the WMS and WWS modified in the fluidized bed

In the course of this series of tests, alkalized WWS and WMS were placed in the fluidized bed (total height approx. 700 mm, inner diameter in the area of the fluidized bed d = 80 mm, glass frit with porosity P2, P100, magnetic vibrator type MV1/100-3 AEG, oscillation rate 6000/min, Fluidization gas nitrogen +2.5% oxygen, volume flow 200 l/h, fluidization speed 11 mm/s and heating rate 12 °C/min) and the functionalized starches obtained are then used as in test series 1 in the production of food preparations. These food preparations were then examined rheologically in order to characterize them theologically on the one hand and to check their storage stability on the other.

The results of the measurements with a fruit preparation (40°Bx, pH4.1) are presented here as an example. The following RWS and WMS modified in the fluidized bed were tested in fruit preparations: RWS 180°C 30' and WMS 180°C 30'. Example 1: Production of fruit preparation

Devices

Stephan universal machine UM/SK 5; Sartorius scales, 2 decimal places

recipe

Components: [%]

A

Strength (in DS) 4.44

Buffer (pH 3.2 or pH 4.1) 30.90

B

potassium sorbate 0.06

Granulated sugar 33.00

C

Strawberry puree 31.60

manufacturing

Production of a starch slurry (A), the other components (B) are weighed in and the strawberry puree (C) is stirred in, now everything is transferred to the Stephan cooker (anchor stirrer, 15% HM, 10% TF), it is heated to 98 ° C and this temperature is maintained for 8 minutes, then it is cooled to 70 °C, then a vacuum of 200 mbar is applied and meanwhile cooled to 30 °C, the finished preparation is transferred into glasses and stored in the refrigerator.

Results rheology

It can be clearly seen from FIG. 4 that the fruit preparation containing the physically modified WMS shows a very even progression, while the fruit preparation containing the physically modified WMS shows a significant increase in the storage modulus G' after 3 weeks. This means that the paste of the WWS is apparently more stable.

Test series 3: Freeze-thaw stability of waxy wheat starch and waxy maize starch physically modified by means of a spiral vibratory feeder

In addition to the attempts to investigate the physically modified WWS and WMS in food preparations, the stability analyzes were supplemented by investigations of the freeze-thaw stability (GT-Stab.).

Production of the functionalized starches

The respective alkalized starches (pH 9.5) were pre-dried until they contained less than 2% moisture. They were then physically functionalized in the previously described oscillating conveyor at 195°C for 30-120 min. Investigation of the freeze-thaw stability of the functionalized WWS and WMS

For this purpose, the functionalized starches were gelatinized and deep-frozen. These paste were then thawed in several cycles and their syneresis was determined by centrifuging the paste and determining the amount of water on the surface. The syneresis corresponds to the relationship between the separated water and the total weight of the paste in percent, with these being added up for each cycle.

Results of the measurements

According to FIG. 5, the functionalized WWS used according to the invention shows only a lower tendency to syneresis both with a 60 min (FIG. 5) and with a 90 min (FIG. 6) functionalization, the highest stability being achieved with a 90 min heat treatment.

Test series 4: enzymatic degradation of waxy wheat starch

480 g of a 20% starch slurry are prepared in a 1000 mL beaker. The pH value of the well-mixed slurry is measured and the sample is then completely transferred to the Brabender measuring pot. Now 24, 48 or 96 mΐ (0.025%, 0.05% or 0.1% on starch TS) Warozym 152A are added and the measurement is started according to the specified measurement program. Immediately after the measurement, approx. 250-300 mL of the paste obtained is transferred to a 400 mL beaker, cooled to 50°C with cold water within 5 minutes and measured at 100 rpm on the Brookfield viscometer. The paste is then further cooled to 25°C and measured again. After a further 24 hours, the viscosity is measured again at room temperature. The pH value of the paste is also determined.

Measuring program

Heating/cooling rate: 3 °C/min

Starting temperature: 30 °C

Maximum temperature: 95 °C

Upper holding time: 30 min

Final temperature: 95 °C

End hold time: 0 min

Load cell 1000 cmg

result

As can be seen in Table 1 of test series 4, the WWS shows significantly lower viscosities under the same reaction conditions and the same use of enzymes, and also a significantly better stability of the viscosity compared to wheat starch. The amount of enzyme can be reduced to about 1/4 of the amount used, but in order to achieve a lower viscosity after 24 hours compared to WS. Due to the lower use of enzymes to obtain a certain viscosity, significantly higher can be achieved with the WWS Molar masses can be achieved, as can be seen in Figure 7 and Table 2 of test series 4, which leads to a higher binding power of the WWS paste compared to WS in the application.

Test series 4, table 7: viscosities

Enzyme Brookfield

TS Brookfield 50°C Brookfield 25°C

24 hours

Strength [% on Strength] [%] [mPa.s] [mPa.s] [mPa.s]

WS ÖjÖ5 87.06 4950 34600 gel-like

WWS 0.05 89.47 166 410 490

WS 0.1 87.06 242 598 1876

WWS 0.025 89.47 432 1072 1366

Test series 4, Table 2: Molar mass distribution data

Mw < 25,000 25,000- 1,000,000 > 1,000,000

[g/mol] [%] [%] [%]

WS 0.05 1480000 25.7 35.4 38.9

WWS 0.05 1730000 12.2 43.1 44.7

WS 0.1 464000 34.4 50.6 15.0

WWS 0.025 3900000 9.4 28.7 61.9

Test series 5: Determination of the freeze/thaw stability of phosphate cross-linked waxy wheat starch in comparison with waxy maize starch

750 g of starch (WMS or WWS, see table below) in DM are made up to 1973.68 g with deionized water (38% slurry). This slurry is heated to 40° C. in a water bath and adjusted to pH 10.5 with 3% NaOH. Then 2.2 g CaCl2 (=2.914 g CaCl2*2H2O) are pre-dissolved in 8.8 g H2O, added and stirred at pH 10.5 for 20 minutes. NaTMP (see table below for weight) was likewise predissolved in water and added to the slurry, and the mixture was stirred at 40° C. and pH 10.5 for 35 minutes. The pH is then adjusted to pH 5-5.2 with 8% HCl. It is drained with the laboratory centrifuge and washed with deionized water until the conductivity of the washing water is below 100pS. Then it is dried in the Retsch dryer.

Both TS 131 and TS 130, as shown in Figure 8, show better freeze-thaw stability with less water separation, at least up to 4 cycles. TS 131 shows a superiority over all cycles as the two other strengths examined. TS 129 and TS130 show mostly similar freeze-thaw stabilities, with TS 130 showing less syneresis initially and more than TS129 after more than 4 cycles.

Batch no. Raw material weight NaTMP [g] % on DS starch

TS125 WWS Waximum 1.9 0.25%

2018

TS126 WMS 1.9 0.25% TS129 WMS 0.8 0.107% TS 130 WWS 0.4 0.053% TS131 WWS 0.25 0.033%

analyses

Freeze-thaw stability of a 4% paste, neutral

Syneresis summed up over all cycles [%]

Number TS 129 TS 130 TS 131

Thawing cycles WMS WWS WWS

1 18.94 18.65 3.92

2 52.79 38.19 11.61

3 73.08 61.85 26.49

4 88.49 86.20 42.76

5 106.45 115.63 65.61

6 122.31 149.44 90.15

Test series 6: Comparison of chemically modified waxy wheat starches with the chemically modified waxy maize starches

Chemically modified waxy wheat starches (WWS) and similarly chemically modified waxy maize starches were produced and their paste stability under the influence of heat and acid was examined. A higher heat stability is reflected in a lower breakdown in the Brabender Viscograph, the higher acid stability can be seen from the higher final viscosity in the acid by measurement in the citrate Brabender (CB) (Examples 1-4 of test series 6, Table 1, Figures 9 to 12 ). Production of the modified starches

The percentages in the recipes always refer to the dry substance weight of the starch, the slurry is prepared with deionized water.

Example 1: Production of acetylated, adipate-crosslinked waxy wheat starch (WWS) and waxy maize starch (WMS) (Modification A, Type E1422)

pattern designations

WWS A, WMS A

recipe

38% (w/w) slurry with WWS or WMS

0.8% (w/w) reaction mixture (1:3 adipic acid & acetic anhydride)

3.3% (w/w) acetic anhydride

implementation of the modification

Preparation Heat the slurry to 30 °C-35 °C

Adjust pH 8-9 with 3% NaOH; Stir for 1 h at 30 °C-35 °C Addition Reaction mixture pH 8-9 with 3% NaOH Add acetic anhydride Maintain pH 8-9 with 3% NaOH

Reduce slurry to pH 5-6 with 8% HCl, drain, dry.

Example 2: Production of acetylated, adipate-crosslinked waxy wheat starch (WWS) and waxy maize starch (WMS) (Modification B, Type E1422)

pattern designations

WWS B, WMS B

recipe

38% (w/w) slurry with WWS or WMS

0.7% (w/w) reaction mixture (1:3 adipic acid & acetic anhydride)

7.4% (w/w) acetic anhydride

Carry out the modification as in example 1 Example 3: Production of acetylated, adipate-crosslinked waxy wheat starch (WWS) and waxy maize starch (WMS) (modification C, type E1422)

pattern designations

WWS C, WMS C

recipe

38% (w/w) slurry with WWS or WMS

1.3% (w/w) reaction mixture (1:3 adipic acid & acetic anhydride)

7.4% (w/w) acetic anhydride

Carry out the modification as in example 1

Example 4: Production of propoxylated, phosphate-crosslinked waxy wheat starch (WWS) and waxy maize starch (WMS) (Modification D, Type E1442)

pattern designations

WWS D WMS D

recipe

38% (w/w) slurry with WWS or WMS

13% (w/w) sodium sulphate

0.03% (w/w) sodium trimetaphosphate (NTMP)

9.8% (w/w) propylene oxide on starch TS NaOH 3% for alkalinization H2SO4 10% for neutralization

implementation of the modification

Preparation Slurry adjust alkalinity to 0.6-1 ml 0.1 N HCl/g slurry with 3% NaOH Heat to 30 °C Add NTMP Add propylene oxide

Keep temperature at 35 °C-40 °C increase pH with 10% H2S04 to pH 4.0-5.0 drain and dry. Analyzes of modified starches

The gelatinization behavior is carried out in an acidic medium using a Brabender Viscograph-E® (Brabender GmbH) according to ARIC method ^B1.9 (Brabender citrate=CB, pH3.5).

The evaluation points that are decisive for the assessment of heat and acid stability are:

Breakdown: Difference between peak viscosity (maximum viscosity in the heating phase) and viscosity at the beginning of the cooling phase (end of holding time at 95°C) as a measure of heat stability

Final viscosity: Viscosity at the end of the cooling phase as a measure of the acid stability of Citratbrabender

Viscosity measurement results

The modified WWS and WMS are subjected to the Brabender reboils and evaluated based on the evaluation points. In the case of the modifications described in Examples 1-4 of test series 6, the chemically modified waxy wheat starches have a higher heat stability and a significantly higher acid stability in contrast to analogously chemically modified waxy maize starch. The higher heat stability is reflected in a lower breakdown. The higher acid stability of the modified waxy wheat starch (WWS) compared to the analogously modified waxy maize starch can be seen from the higher final viscosity in the citrate brabender (CB) (Examples 1-4 of test series 6, Table 1, Figures 9 to 12). This advantage is reflected in the modifications A to D, which covers a wide variation of the modification.

Test series 6, Table 7: Evaluation points after modification A mod. Starches in an acidic environment (CB) Test series 7: Production of Starch Blends and investigation of the synergetic effects of the mixtures

The starch mixtures created according to a mixture test plan, here made from potato, corn, waxy corn or waxy wheat starch, were examined for their Brabender viscosity developments, their rheological behavior and their texture. Here, surprising differences between the two wax-starch types could be determined due to synergetic effects. Above all, the higher acid stability and the formation of firmer paste under acidic conditions is a surprising result with waxy wheat starch.

Production of starch mixtures (blends)

The blends were made from native starches according to a test plan (Figure 13) from 3 native starches each. The native starches were mixed in a two-axis mixer (Collomix GmbH) with a mixing time of three minutes, at 70 rpm horizontally and 10 rpm vertically. The dry substance of the native starches in the mixtures was taken into account in the weights. The desired final weight per blend was 500 g dry substance. Figure 13 shows the test points in mixture design 1 and 2. The experiment plan on the left (experiment plan 1) shows the simplex lattice experiment plan with the three components MS (corn starch), KS (potato starch), WMS (waxy corn starch), the right image (experiment plan 2) shows the simplex lattice experiment plan with the three components MS (corn starch), KS (potato starch), WWS (waxy wheat starch).

Method Brabender

Weigh 30 g dry substance of a native starch blend with 450 g liquid in a 600 mL beaker and mix. Each starch blend was filled up to 480 g with deionized water for the Neutraibabender (NB) and with citrate buffer (pH 3.5) for the Citratbrabender (CB) and then with a laboratory spoon for further use in the viscometer (Viscograph - E, Brabender). The starch blends to be examined were gelatinized in deionized water or with citrate buffer (pH 3.5) in order to show the influence of the pH value on the properties of the native starch blends.

Results Brabender

If one compares the two test plans, surprisingly higher peak viscosities result than with waxy maize starch, especially with high amounts of potato starch (> 66.67%) or with mixtures of the three native starches with waxy wheat starch (Table 1 of test series 7). Under neutral conditions, the waxy wheat starch has higher final viscosities than the waxy maize starch (Table 2 of test series 7). Test series 7, Table 7: peak viscosities of the blends

Test series 7, Table 2: Final viscosity of the Blertds

Results rheology

The level of the yield point provides information about the strength of the paste obtained. It is defined as the intersection of G' and G", also called crossover. Beyond this point, the internal structure of the sample shows an irreversible change.

When comparing the two types of wax and starch, surprising differences can be identified. The crossover values of pastes with waxy wheat starch are higher than those with waxy maize starch for mixtures of three native starches, with the use of > 50% corn and potato starch (Table 3 of test series 7). Test series 7, Table 3: Cross-over values of the blends

The comparison of the mixtures of the three native starches from test plans 1 and 2, using corn and potato starch with > 50%, also shows higher loss moduli (G") in test plan 2. This means that waxy corn and waxy wheat starch in combination with Corn or potato starch have the same rheological properties, but in combination with > 50% corn and potato starch, the mixtures with waxy wheat starch form the stronger paste (Table 4 of test series 7).

Test series 7, Table 4: Loss moduli of the blends

Brookfield viscosity of starch paste

After a storage time of 24 hours at 4° C., the viscosity of the gels was measured using a viscometer (Brookfield Ametek DV-1, Ametek. Inc. Brookfield). The spindle size of the Brookfield viscometer was adjusted to the strength of the gels. The values obtained show the dynamic viscosity in mPa.s. As can already be seen from the final viscosity, there are clear differences in the strength of the products obtained between Citratbrabender and Neutraibabender.

An interesting difference in viscosity is found in mixtures containing 75% cornstarch and 25% waxy starch (25/75/0). In an acidic environment with large amounts of corn starch, waxy wheat starch forms firmer internal networks than waxy corn starch (Table 5 of test series 7).

Experimental series 7, Table 5: Brookfield viscosities of the blends

Experimental series 8: Thermal functionalization of alkalized waxy maize starch and waxy wheat starch and LM-AWT investigations

Waxy maize starch (WMS, F5) and waxy wheat starch (WWS, F6) were thermally functionalized under the same conditions at 175 °C for 60 min in a Revtech system and the products were comparatively characterized. The starting materials were previously made alkaline to a pH of 8-10 with sodium hydroxide solution, dried and ground.

Production and testing of food preparations

The two functionalized WMS (F5) and WWS (F6) were tested in strawberry fruit preparations at two pH levels of 3.2 and 4.1. A total of 4 applications were made in this way. The fruit preparations were manufactured sterile and filled in sterile form for storage. Example 1: Production of strawberry fruit preparation

The strawberry fruit preparations were each made with the modified starches WMS (F5) and WWS (F6) according to the following recipe and filled into sterile screw-top jars for later theological measurements.

The following items were sterilized in the autoclave:

4 sterile 1L Schott jars

60 sterile 50 mL screw-top jars

Various spatulas and spoons for filling the samples

Equipment/Materials

Stephan universal machine UM/SK 5 Sartorius scales Various beakers Various spatulas and spoons 150 mL screw-top jars 1 sterile 1 L Schott glass 15 sterile 50 mL screw-top jars Memmert UF110 climate cabinet

recipe

components [wt. %] [g]

A strength (in dry matter) 4.44 134.19

Buffer (pH 3.2 or 4.1) 30.90 933.87

B potassium sorbate 0.06 1.81

Granulated sugar 33.00 997.33

C strawberry puree 31.60 955.02

Total 100.00 3022.22

preparation

A starch slurry was produced from components A in a beaker. The other components B were weighed in and the strawberry puree C was stirred in. The mixture was transferred to the Stephan cooker (anchor stirrer, 15% HM, 10% TF), heated to 98° C. and maintained at this temperature for 8 minutes. Then it was cooled down to 70 °C. Finally, a vacuum of 200 mbar was applied while cooling to 30°C. bottling and storage

Each of the 4 preparations was sterilely filled in a laminar workbench and then stored in a climatic cabinet at 35°C.

Rheological measurements

The measurements served the theological characterization of the samples in food systems. These measurements were measured and evaluated with the Physica MCR-301 rheometer from Anton Paar at a pH value of 3.2 and a temperature of 175 °C for 60 min in rotation and oscillation. The amplitude sweep was performed at 1 Hz while varying the deformation from 0.1 -100%. The frequency sweep was carried out by varying the frequency from 0.1-30 Hz, the selected deformation was chosen depending on the linear-viscoelastic range determined in the amplitude sweep. The food preparations were stored at 35° C. and measured theologically after 24 h and after 1-5 weeks in order to be able to determine the storage stability. A high storage stability is shown when the rheological parameters such as storage modulus G' (elastic portion), loss modulus G" (viscous portion) and loss factor (tanδ= G"/G') remain the same.

Results of Theological Measurements

The loss factor (tanö= G"/G') is an important rheological parameter that describes the relationship between loss modulus G" and storage modulus G'. The higher the dissipation factor, the more closely the behavior of the sample resembles that of a liquid with Newtonian flow behavior. On the other hand, if the loss factor is small, the behavior of the sample corresponds to that of an ideally elastic solid. It can be seen that with respect to this factor, the strawberry fruit preparation prepared with the physically modified WWS at pH 4.1 (WWS F6, pH 4.1) surprisingly shows a more even flow when stored at 35°C than the physically modified WMS (WMS F5, pH 4.1), which shows a significant increase in relative loss factor after 3-5 weeks (Figure 14). This relative loss factor serves to clarify the changes over the storage period and refers here to weekly relative values compared to the respective starting values at week 0.

Sensory Analysis

The strawberry fruit preparations WWS F6 and WMS F5 stored for 6 weeks, each stored at a pH value of 3.2 and 4.1, were measured sensory using RATA (rate all that applies). The results were compared to those of freshly prepared strawberry fruit preparations. There were 2 sensory panels with 17 panelists.

The following descriptors were requested and should be rated by the panellists on a scale of 1-3 (low to high intensity) or with 0 (not applicable):

Appearance/Texture (non-oral): Gloss, syneresis, smoothness (appearance), turbidity, stability (spreadability), ephemerality, elongation, viscosity Mouthfeel (oral): Homogeneity, fullness (cohesiveness), smoothness, acrid/burning sensation, mouth coating, stickiness, mucus

Taste/aroma (oral): off-flavor

Only the significant descriptors (p-value <0.05) were used for the evaluation. Figure 15 shows the difference in the mean values of the significant descriptors between fresh fruit preparations and those stored for 6 weeks at 35 °C (pH 4.1). A difference between the WWS and the WMS can be seen particularly in the case of short-livedness. It changes primarily in the WMS, while the change is much smaller compared to the same fruit preparation containing WWS. This result of the sensors underlines the findings of the theological measurements and confirms the increased stability of the WWS.

Claims

Expectations

1. Use of waxy wheat starch as a viscosity improver in a liquid or viscous composition, characterized in that the viscosity-improved composition shows a substantially uniform course of the storage modulus G' over a period of 6 weeks.

2. Use according to claim 1, characterized in that the waxy wheat starch is a physically modified waxy wheat starch.

3. Use of waxy wheat starch according to one of the preceding claims in a liquid or viscous composition with a viscosity of more than 10,000 mPa.s at 20°C, characterized in that the composition has a pH in the acidic range.

4. Use of waxy wheat starch according to one of the preceding claims in liquid or viscous foods.

5. Use of waxy wheat starch according to either of claims 3 or 4, characterized in that the pH of the composition is between 3.0 and 6.5.

6. The use of waxy wheat starch as claimed in any of claims 2 to 5, characterized in that the waxy wheat starch was physically modified at a product temperature of between 150 and 200°C.

7. Use of waxy wheat starch according to one of claims 2 to 5, characterized in that the waxy wheat starch was physically modified at a product temperature between 165 and 190°C.

8. Use of waxy wheat starch according to one of claims 2 to 5, characterized in that the waxy wheat starch was physically modified at a product temperature between 175 and 180 °C.

9. Use of waxy wheat starch according to any one of claims 2 to 8, characterized in that the waxy wheat starch has been physically modified during a treatment period of 15 to 120 minutes.

10. Use of waxy wheat starch according to any one of claims 2 to 8, characterized in that the waxy wheat starch has been physically modified during a treatment period of 30 to 105 minutes.

11. Use of waxy wheat starch according to any one of claims 2 to 8, characterized in that the waxy wheat starch has been physically modified during a treatment period of 60 to 90 minutes.

12. Use of waxy wheat starch according to any one of claims 2 to 11, characterized in that the waxy wheat starch has been physically modified in a spiral vibrating conveyor.

13. Use of waxy wheat starch according to any one of claims 2 to 12, characterized in that the waxy wheat starch has been physically modified in a fluidized bed oven

14. Use of waxy wheat starch according to any one of claims 4 to 14, characterized in that the food is selected from mayonnaise, confectionery cream and fruit preparations.