JPH0516819B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to starch-containing thickeners whose aqueous sols are characterized by excellent low temperature stability as demonstrated by their resistance to repeated freezing and thawing cycles. The present invention also relates to foods containing this thickener. Starch generally contains two types of polymers: a linear type known as amylose and a branched polymer type known as amylopectin. Waxy starch, made from grains such as waxy maize, waxy rice and waxy sorghum, has a significantly higher amylopectin content than regular corn starch, making it ideal for applications where starch acts primarily as a thickener or stabilizer and for stability against aging. This is particularly valuable in applications where a neutral sol is desired. To meet the food industry's high demands on food quality, processing, packaging and distribution, natural waxy starches are often used to change the behavioral properties but essentially retain the caloric value of natural (non-gelatinized) starches. It is processed by various known methods to do so. One type of processing commonly used in the industry is starch cross-linking. When an aqueous dispersion of natural starch is heated, the starch granules begin to swell, and the dispersion develops a short, ointment-like texture, which is essential for imparting good texture and thickening food systems. texture). However, during the process of baking natural starches, this texture changes rapidly, especially in the case of waxy starches, becoming elastic and rubbery when the swollen granules are broken. Cooking time, temperature, concentration and shear force and PH
A small change in is sufficient to cause this change. Cross-linking modification acts to strengthen the granules by strengthening the hydrogen bonds that serve to hold them together. Thus cross-linking modification is used to overcome the extreme sensitivity of swollen starch granules to handling and processing conditions. Aqueous dispersions of cross-linked starches are often used under conditions of long term storage at relatively low temperatures and/or occasional exposure to freeze and thaw cycles. Thus, starch dispersions are used in fruit pie fillings (which are often canned) as well as in many frozen foods such as frozen pies, soups, etc. In the case of canned food products, these are often stored in warehouses without heating facilities and are therefore kept at very low temperatures for long periods of time. Frozen foods are also stored at very low temperatures for long periods of time. Under such conditions of low temperature exposure, a distinct reduction in the hydrating power of the starch present in such food products occurs, thereby leading to syneresis or leaching of liquid, and a noticeable change in texture, color and transparency. This will cause severe deterioration. Although waxy starch sols are more stable than regular starch sols, they tend to form intermolecular associations during storage at or near freezing temperatures. Attempts to overcome this problem have traditionally been
Substituted branches can be introduced into the starch molecule by various chemical derivatization reactions, for example by reacting the starch with monofunctional reagents to introduce substituents such as hydroxypropyl, fonefuate, acetate or succinate groups. It was related. Such substituents improve the starch by preventing association between molecules or parts of the same molecule, i.e. reducing the tendency of the substituted starch to lose its hydrating power and transparency, especially during storage at low temperatures. Stabilize. These derivatization reactions can be carried out alone on natural starches to improve their low temperature stability, but are often carried out in combination with cross-linking for use as thickening agents in canned pie fillings, retort puddings, etc. Provides starch. This prevents the food from losing its transparency and texture during winter storage or transportation and freezing. In recent years, research has been conducted to create starch that has all the properties of modified starch without chemical treatment. US patent
No.3525672 (August 25, 1970, OBWurzburg
et al.) inhibited starch by enzymes such as β-amyl-
However, this is not currently a viable method. The present invention provides a thickener containing starch, the sol of which exhibits the low temperature stability of chemically stabilized waxy starch. Furthermore, the present invention provides a starch-containing thickener that is particularly suitable for making food products with good low temperature stability. This improved thickener composition combines water and wxsu2
Contains starch from plants of the (homozygous) genotype. This starch is characterized by having a sol that can withstand at least one freeze-thaw cycle than the sol of natural waxy starch from a corresponding plant that is not of the wxsu2 genotype. The mutant waxy starch from the plant species selected in the present invention can be native or derivatized and/or cross-linked and has less sol than the common normal natural waxy starch from the same plant species. Both have sols that withstand one freeze-thaw cycle. In making the thickener composition of the present invention, this particular starch is mixed with any suitable proportion of water depending on its end use, and the mixture is then cooked if necessary. If starch is processed and becomes “cold water swellable”
If so, shoe kinging is not necessary. In forming the thickener, about 1 to 20% by weight of starch
Mixing with ~99% water by weight generally gives satisfactory results. However, proportions outside this percentage may also be satisfactory in some applications. It is to be understood that the present invention encompasses not only thickeners containing starch, but also thickeners containing flour or ground products from plants such as ground corn, ground corn and meal. The sugary-2 genotype (designated su2) is known to alter the carbohydrate composition of maize endosperm, and a double recessive mutant of the waxy (designated wx) sugary-2 genotype is also known to alter the carbohydrate composition of maize endosperm. ing. However, it is completely unexpected that the starch sols obtained from the waxy sugary-2 genotype have better resistance to property degradation at low temperatures than the corresponding normal natural waxy maize starch sols. It happened. The latter starch survives only about one freeze-thaw cycle before losing its water-binding properties, gelling, and exhibiting syneresis.
The properties obtained in the compositions of the present invention have heretofore been obtained only by chemically derivatizing waxy starch with monofunctional reactants. The derivatization required to provide the compositions of the invention with exceptional freeze-thaw properties is less than that required for waxy starch. The thickener compositions of the present invention may be advantageously used in any food product in which natural or crosslinked or derivatized or crosslinked-derivatized starches are used, such as puddings, pie fillings, sauces, gravies, baby foods, etc. I can do it. However, it is particularly suitable for use in foods that are to be stored at low temperatures and in frozen foods. The use of waxy starch is also particularly preferred in applications where the starch primarily functions as a thickener or stabilizer. In a preferred embodiment, the starch used in the thickener of the invention is designated wxsu2.
It is obtained from maize grown from a double recessive mutant of the waxy sugary-2 genotype. The waxy gene is located at position 59 on chromosome 9 in corn;
The sugary-2 gene is located on chromosome 6 at position 57 (MGNueffer, L. Jones and M. Zuber, “The
“Mutants of Maize”, Crop Science Society of
America, Madison, WI, 1968, p. 72 and 73). Also, wx and/or su2 genotypes are obtained from wxsu2 mutants in which the wx and/or su2 genotypes have been transferred to other locations in the plant genome by translocation, inversion or any other method of chromosome engineering. Starch is also suitable for the present invention. In addition, starch obtained from plants grown from artificial mutants and variants of the above-mentioned gene arrangements, which can be made by known standard methods of mutation breeding, can also be used in the present invention. In the present invention, what is intended as the wxsu2 genotype refers to a mutation that essentially includes the wx and su2 genes, but is not limited thereto. The waxy genotype gives the corn plant the ability to make starch consisting primarily or entirely of amylopectin, and the endosperm and phenotype or physical expression of the waxy genotype is opaque with a hard waxy texture. On the other hand, the endosperm phenotype of the sugary-2 genotype is translucent and sometimes wrinkled. R. Creech's research results on the effects of sugary-2 and waxy gene mutations, alone and in combination, on maize endosperm and its properties are published in Advancee in Agronom, Vol. 20.
(Academic Press, 1968), p275-332 and
Genetics, 52, p1175-1186 (December 1965). “The Effects of Genetic” by RMStandstedt, BDHites, and H. Schroeder.
Variations In Maize On tne Properties of
the Starches”, (Nebraska Agricultural
Experiment Station, published as paper no. 1894) describes some properties of starch obtained from various mutants of maize containing wxsu2. The data in this paper indicate that the particular wxsu2 starch used therein has greater sol stability to heat and lower gelatinization temperature than wx, but such properties are combined with superior low temperature stability. It does not imply sex. Starch obtained from mutant maize has also been described in “Gene Interactions In Maize Affecting” by HHH Ramer et al.
Endosperm Properties”, Agron.J., 50, p207
~210 (1958), is also described. To obtain double recessive mutants of the wxsu2 genotype in maize in the usual way, e.g.
If a waxy mutant (wx) is crossed with a sugary-2 mutant (su2) and then self-pollinated to produce a single generation single hybrid (Wx wx Su2 su2), theoretically Double recessive mutants can be recovered at a ratio of 15:1. The starch used in the present invention can be obtained from inbred sequences, but more preferably the starch is derived from inbred strains containing wxsu2 double recessive mutants, due to usually higher yields and other factors. Obtained from hybrids produced by Although maize is a preferred particular plant of the present invention as a source of waxy starch, other plant species such as waxy rice, waxy barley, and waxy sorghum are also suitable as long as they are of the wxsu2 genotype. Extraction of starch from maize kernels grown from double recessive mutant seeds can be carried out in standard manner by, but not limited to, wet milling or dry milling processes known in the art. isn't it. In a typical wet milling process, preferred in the present invention but only by way of example, the cone is cleaned with a strong air stream, a sieve, and a magnet to exclude undesirables. The corn is then soaked in warm water containing a small amount of sulfur dioxide. Drain the soaking water and pass the softened grain through a friction mill to break it up. Remove the embryos, grind and wash the remaining mixture,
Sieve as slurry. The starch is separated from the gluten by centrifugation, and the remaining slurry starch is then filtered, washed, resuspended, and refiltered. The extraction of fine flour or its variants from maize grain is carried out in a light milling process. Suitable in the present invention, but without excluding other procedures,
In a typical such procedure, the corn is first thoroughly cleaned and then passed through a mulch.
It is then tempered or conditioned and passed through a corn embryo removal machine.
The material from the embryo removal machine is dried, then cooled, passed through a grinder and suction device, ground, and finally sieved depending on whether whole fractions or separate fractions are desired. . In any of the extraction processes described above, it may be desirable to make some modifications, such as using lower soaking temperatures than normally used,
It will be understood that those skilled in the art can easily think of this. The starch or flour thus obtained is tested for its properties at low temperatures in the usual manner.
At that time, a sol is formed as described below. The starches of the present invention can be derivatized, if desired, by known methods, such as to form ethers or esters such as hydroxypropyl ale, acetate, phosphate, succinate, such as octyl succinate, tertiary and quaternary amine ethers, etc. or by any other modification method that produces a starch with the properties defined herein. Preferred substituents here are hydroxypropyl, phosphate or acetate groups. For industrial purposes, the modification of starch preferred in the present invention is in order to make the granules tougher against the handling and processing conditions often encountered during manufacturing operations and to produce starches that can impart desirable ological properties to food systems. It is to crosslink. Any crosslinking agent may be used for this purpose, such as epichlorohydrin, linear dicarboxylic acid anhydrides, citric acid, acrolein, phosphorus oxychloride and trimetaphosphate. Other known crosslinking agents such as formaldehyde, cyanuric chloride, diisocyanates, divinyl sulfone, and any other crosslinking agent capable of forming crosslinks between starch molecules can also be used unless the product is used in a food product. Preferred crosslinking agents are those approved for use in food products, most preferably phosphorous oxychloride, sodium trimetaphosphate (STMP) and adipine-acetic anhydride (1:4). The cross-linking reaction itself has been described in the literature for making cross-linked granular starches, for example US Patent No. 238537 (GE
Felton et al., September 7, 1943) and No. 2801242
(RW Kerr et al., July 30, 1957). Performed according to standard procedures as described in the specification. The amount of crosslinker required to give a suitable product depends on, for example, the type of crosslinker used, the crosslinker concentration,
It will vary depending on the reaction conditions and the need to obtain a crosslinked starch that falls within the desired viscosity range. Those skilled in the art will readily recognize what amounts may be used, as is known in the art. Typically, this amount ranges from as low as about 0.001% by weight of starch weight to as high as is considered acceptable for food applications. In the following examples, parts and percentages are by weight unless otherwise specified. The following analytical tests are used in the examples to evaluate the low temperature stability of the starches (or flours) of the present invention. Evaluation of the low temperature stability of the starch of the present invention usually involves its storage at low temperatures for long periods of time. However, in order to obtain a more rapid and relatively accurate assessment of low temperature stability, freeze-thaw tests were now initiated. 50 g of 12% moisture starch (3.3 g anhydrous)
Make a starch sol by mixing with ml of distilled water. Add this starch slurry to 0.1N HCl or
Adjust the pH to 5.0-6.0 with 0.1N NaOH and add two drops of McCormick red food coloring to it. The slurry is boiled in boiling water with stirring for 20 minutes until the starch granules are swollen. Put the starch sol thus obtained into a 2 ounce jar, cover it with a lid,
0〓 (-18℃) and placed in a freezer for about 66 hours. After the end of the first freezing period, the sol is thawed at room temperature (6 hours), examined and refrozen for a second cycle (18 hours). The freezing time (18 hours) and thawing time (6 hours) are repeated for 3rd, 4th and 5th cycles. The 6th cycle requires a 66 hour freezing period and the 7th to 10th cycles require an 18 hour freezing period. The test will either separate the water and form a gel, or the gel will not form yet but the sol will become opaque and its color will become pink or the viscosity and/or texture will change significantly (e.g. low viscosity and grainy). ) can be continued until This latter condition is a matter of degree. The number of successfully completed cycles before the sol is damaged is recorded for each sample. Note that this test is for a relative indication of stability and controls are tested for each material. Example 1 This example illustrates the better low temperature stability of the natural and derivatized starches of the present invention compared to natural and derivatized waxy maize starches. The starches listed in Table 1 are obtained by wet milling one of the given starch sources. The low-temperature stability of each starch was evaluated using the procedure described above, and the results are shown in Table 1.
Shown below.

【table】

[Table] From these results, the natural starch sol of the present invention is
It exhibits better freeze-thaw properties than sols of natural waxy maize starch and even sols of acetylated waxy maize starch. It is also clear that all three sources of sugary-2 gene tested provide starch (starch thickener) with excellent freeze-thaw properties. It is also known that the cross-linked starch of the present invention has better low temperature stability than that of cross-linked waxy maize, and that the cross-linked derivatized starch of the present invention has a lower temperature stability than that of cross-linked waxy maize that is derivatized to the same extent. It turns out to be much more stable. In fact, the crosslinked derivatized starch of the present invention has the same or better low temperature stability as the more highly derivatized crosslinked waxy maize. Also, the underivatized cross-linked starches of the present invention have the same or better low temperature stability as cross-linked waxy maize derivatized with up to 5% propylene oxide. These results were unexpected given one of the known purposes of using derivatizing agents: improving the low temperature stability of starch. Example 2 Natural starch obtained from wxsu2A in temporally modified OH7 embryo plasma was added to high and low PH
into a salt aqueous solution and stir. A flavor test was conducted on the starch slurry obtained, and it was found that the starch slurry had a low pH even at high pH.
However, starch was found to have no negative effect on the flavor of the slurry. Example 3 Two cherry pie fillings are made using the same ingredients and amounts, except that one contains 0.01% starch.
% phosphorus oxychloride crosslinked waxy of the present invention
sugary-2 mutant starch, the other was derivatized with 5% acetic anhydride and 0.12% for comparison.
Waxy maize crosslinked with adipic acid-acetic anhydride is used. when subjected to 10 or more freeze-thaw cycles (each cycle comprising freezing overnight at 17°C (-8.3°C) and then thawing for 6-7 hours);
Cherry pie fillings made with natural waxy sugary-2 mutant starch are more stable than pie fillings made with derivatized waxy starch. The latter survives only 6 freeze-thaw cycles. Both pies have good appearance, flavor and texture. Example 4 In the production of tomato sauce, 6 peeled whole tomatoes are passed through a sieve to separate the tomato pulp from the juice. The tomato juice thus obtained is slurried with the starch of Example 2 (in an amount of 1.8% by weight relative to the total sauce weight). The resulting slurry is thickened until thickening (thickening) occurs. Then add the tomato pulp and seasonings and continue cooking until the desired consistency of texture and consistency is achieved. The resulting tomato sauce was found to be stable after repeated freezing and thawing cycles. In the production of frozen brown gravy,
Thoroughly mix the following ingredients and reduce the mixture to 190%
(87.8℃). Beef broth 62.6% Water 24.3% Starch of Example 2 3.0% Flour 2.0% Salt 1.4% Sodium glutamate 0.4% Spices 1.2% Slowly add 5.1% of the melted vegetable shortening to the hot mixture under constant stirring and add 190% ~195〓
(87.8-90.6°C) Continue shoeking for 8 minutes.
If desired, add brown dye to the gravy, pack the gravy into containers, and freeze. The resulting brown gravy was found to be stable upon repeated freezing and thawing cycles. In the production of frozen pudding (butterscotch), the following ingredients are thoroughly mixed. Starch of Example 2 19.0% Sugar 40.0% Maltodextrin 20.0% Non-fat dry milk solids 0.1% Salt 0.9% Butterscotch flavoring Appropriate amount Part of the above mixture 22.35% and 47.65% water and
Add 30.00% cream substitute. Heat the mixture to 185-190〓 (85-87.5°C) with good stirring and keep at this temperature for 10-15 minutes. Pack the resulting pudding into containers and freeze. It can withstand repeated freeze-thaw cycles. A starch-containing thickener is produced, the starch sol of which is characterized in that it is colder stable than that obtained using chemically stabilized waxy starch. The thickener composition can be used in addition to food applications, for example in pints, pastes or adhesives, and is preferably used as a thickener or stabilizer for various food products.

Claims (1)

[Scope of Claims] 1. wxsu2 genotypes, translocations, inversions, mutations and mutations thereof that can withstand at least one freeze-thaw cycle more than sols of natural waxy starch from corresponding plants that are not of the wxsu2 genotype. A thickened cold food product comprising: a sol comprising an effective amount of waxy starch from a plant of water; and at least one food product. 2. The food according to claim 1, wherein the starch is waxy maize starch. 3. The food according to claim 2, wherein the starch is natural (non-gelatinized) starch. 4. The food according to claim 2, wherein the starch is crosslinked. 5. The starch is crosslinked using a crosslinking agent selected from the group consisting of epichlorohydrin, linear dicarboxylic acid anhydrides, acrolein, phosphorous oxychloride and trimetaphosphate in an amount of at least 0.001% by weight relative to the weight of starch. Foods listed in scope item 4. 6. The food according to claim 2, wherein the starch is derivatized and contains a substituent. 7. The food according to claim 6, wherein the starch is derivatized with a suitable reagent to form hydroxypropyl ether, phosphate, octenyl succinate, acetate or tertiary or quaternary amine ether. . 8. The food according to claim 2, wherein the food is pie filling, tomato sauce, gravy, or pudding.