JPS6098952A - Starch thickener having improved low temperature stability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a starch-containing thickner whose aqueous sol is characterized by excellent low temperature stability as demonstrated by its resistance to repeated freezing and thawing cycles. do. 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 turmeric, has a much higher amylopectin content than regular cornstarch, and has a high content of amylopectin, which makes it difficult to use and age where the starch primarily acts as a thickener or stabilizer. It is particularly valuable in applications where a stable sol that resists is desired.

In order to meet the great demands of the food industry regarding food quality, processing, packaging and distribution, natural waxy starch is used to improve the natural waxy starch, which changes its behavioral properties but essentially reduces the caloric value of the natural (non-gelatinized) flour. The VC can be processed by various known methods to retain it.

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 the crispiness that is essential for imparting mouthfeel and thickening food systems (5).
hort) % Ointment-like texture (texture)
develop. 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. Small changes in cooking time, temperature, concentration and shear force and pH are 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, abrasiveness is used to overcome the extreme rc sensitivity of swollen starch granules to handling and processing conditions.

Aqueous dispersions of cross-linked starches are often used under conditions of storage at relatively low temperatures for long periods of time 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 hydration capacity of the starch present in such food products occurs, thereby leading to 7nerysis or liquid leaching, and also to changes in texture, color and transparency. Significant deterioration occurs. Although waxy starch sols have superior stability compared to ordinary starch sols, they tend to form intermolecular associations during storage at or near freezing temperatures. Attempts to overcome this problem have traditionally relied on various chemical derivatization reactions, such as reacting starch with monofunctional reagents to introduce substituents such as human mixipropyl, phosphate, atentate or succinate groups. Yoru,
It was associated with the introduction of substitutional branches into the starch molecule. Such substituents improve the quality of starch by preventing association between molecules or between parts of the same molecule, especially during storage at low temperatures, i.e. by reducing the tendency of the substituted starch to lose its hydration and transparency. 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 to be used as thickening agents in canned pie fillings, retort puddings, etc. Gives 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 352567
2 (197 (1 year, August 25, O, E, Wurgb
(Ug et al.) disclose treating inhibited starch with enzymes such as β-amylase to impart freeze-thaw stability to it, but 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 (
thickner).

This improved thickener composition contains water and starch from plants of the wxsu2 (homozygous) genotype. This starch is characterized by having a sol that can withstand at least one freeze-thaw cycle, as does 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 can also be used as a solubility of the common normal natural waxy starch from the same plant species. Having a sol that withstands at least 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 the starch has been processed and is "cold water swellable", then shoeing is not necessary.

In forming the thickener, generally satisfactory results are obtained by mixing about 1 to 20 weight percent starch with about BO to 99 weight percent water. However, proportions outside this percentage range 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 corn, ground corn and meal. .

The sugar-2 genotype (denoted as su2) is known to alter the carbohydrate composition of the noisy endosperm, and waxy (denoted as WX) eugary-2
Genotypic double recessive mutants are also known. However, it is completely unexpected that the starch sol obtained from the waxy sugar -2 genotype has better resistance to property degradation at low temperatures than the corresponding normal natural waxy starch sol. Was that. The latter starch survives only about one freeze-thaw cycle before losing its water-binding properties, gelling, and exhibiting syneresis. The properties obtained with the compositions of the present invention have heretofore been obtained only by chemically derivatizing waxy starch with monochrome reagents.11 The compositions of the present invention have exceptional freeze-thaw properties. Less derivatization is needed to feed the waxy starch than that required for waxy starch.

The thickener compositions of the present invention are 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 starches, etc. It is particularly suitable for use in foods to be stored at low temperatures and 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 waxy, designated wxsu 2.
Obtained from noise grown from a double recessive mutant of the sugar-2 genotype.

The waxy gene is located at position #59 on chromosome 9 in corn, while the eugary-2 gene is located at position #57 on chromosome 6.
(M, G, Nueffer, L,
Jones and M. Zuber = The Mu
tants of Maize-.

0rop 8cienae 8ociety of A
merica, MadiBon.

(See W. Eng., 1968, p. 72 and 76).

In addition, wx and/or su 2 genotypes are translocated (tra
nslooation), inversion (1nverson)
) or transferred to other locations in the plant genome by any other method of chromosome engineering and obtained from the ft-vtxtsu2 mutant are 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. wx here
Designation of a mutant designated as a su2 genotype means, but is not limited to, that the mutant necessarily contains the WX and su2 genes.

The WaX7 genotype gives corn plants the ability to make starch consisting primarily or entirely of amylopectin, and the phenotypic or physical expression of the endosperm of the waxy genotype is
It has a hard wax-like texture and is opaque. On the other hand, su
The endosperm phenotype of the gary-2 genotype is translucent and sometimes wrinkled. θugary-2 and Wa
RoOre on the effect of each X7 gene mutation alone and in combination on noise endosperm and its properties.
ech research results, Advances in Ag
ronomi.

Vol, 20 (Academic Press,
1968), p275-352 and Genetics
, 52, p. 1115-1186 (December 1965)
has been reported. R,M.

8tandedt, B, D, Hltes
, and H,E? “The F!f” written by Chroeder
fects of Genetic Variation
nsIn Maize On the Property
ies of the 5 tarches (Nebra
ska Agricultural Experiment
nt day tation.

(published as paper no. 1894) is wxe
Some properties of starch obtained from various mutants of maize, including u2, are described. The data in this paper indicate that the particular wxeu2 starch used has greater sol stability to heat and lower gelatinization temperatures than WX starch; properties do not imply superior low temperature stability. The starch obtained from the mutant noise is also H,H,Krame
R et al. “Gene engineering interaction n M
aize Affecting Knaoepsrm P
properties', Agron, J., 50.
It is also described in p. 207-210 (1958).

In order to obtain WXθu2 genotype genotypic mutants in noise in the usual way, for example waxy mutant (WX) k sugary-2 mutant (
su 2 ) and then cross-crossed with a single-generation single hybrid (WX
When white flowers are pollinated with WX Su 2 su 2 ), it is theoretically possible to recover double recessive mutants at a ratio of 15:1 from hybrid separated panicles.

Although the starch used in the present invention can be obtained from an inbred sequence, it is preferred that the starch be obtained from an isogenic sequence containing the WX8u 2 double recessive mutant, because of its usually higher yield and other factors. Obtained from hybrids derived from hybrids. Although Nois is the 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 wx
Only those with the su2 genotype are suitable.

Extraction of starch from Noise grains grown from double recessive mutant seeds can be carried out by standard or non-limiting wet milling or dry milling processes known in the art. It's not something you can do. Typical wet type IJ preferred in the present invention but by way of example only
In the cleaning process, the cone is cleaned by strong air currents, sieves and magnets 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. The embryos are removed and the remaining mixture is ground, washed and sieved as a slurry. The starch is separated from the gluten by centrifugation, and the remaining slurry starch is then filtered, washed, resuspended, and
It is then refiltered.

The extraction of fine powder or maize variants from maize grain is carried out in a dry milling process. In a typical such procedure, which is suitable for the present invention but does not exclude other procedures, the cone is first thoroughly cleaned and passed through a strainer, and then tempered or 1. The material from the embryo removal machine is conditioned and passed through the cone embryo removal machine, then it is cooled, ground through the grinder separator and suction device, and finally, the whole fraction is Separate fractions are sifted according to one's wishes.

In any of the extraction processes described above, some modifications may be desirable and can be easily devised by those skilled in the art, such as using lower soaking water temperatures than are normally used. will be understood.

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 used, if desired, in the formation of ethers or esters such as hydroxypropyl ethers, acetates, phosphates, succinates such as octyl succinate, tertiary and quaternary amine ethers, etc. or by any other modification method that produces starch with the properties defined herein. Preferred fFl groups here are hydroxypropyl, phosphate or acetate groups.

For this purpose, the modification of starch preferred in the present invention makes the granules tougher against the handling and processing negatives often encountered during manufacturing operations and to produce starches that can impart desirable rheological properties to food systems. It is cross-linked for this purpose.

Any crosslinking agent may be used for this purpose, such as epichlorohydrin, linear dicarboxylic acid hydroxide, citric acid, acrolein, phosphorus oxychloride and trimetaphosphate. Other known crosslinking agents such as formaldehyde,
Cyanuric chloride, diisocyanate, divinyl sulfone,
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 phosphorus oxychloride, sodium trimetaphosphate (MP below 8) and adipine-acetic anhydride (MP below 8).
4).

The cross-linking reaction itself has been described in the literature for making cross-linked granular starches, for example US patent Nh2528537 (G, Ei,
Fslton et al., September 7, 1943) and the same 2
801242 (R.W. Kerr et al. 19577
March 30th) according to the standard procedure described in the specification.

The amount of crosslinker needed to give a suitable product will vary depending on, for example, the type of crosslinker used, the crosslinker concentration, the reaction conditions and the need to obtain a crosslinked starch 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 α001 weight of starch mass to as high as is considered acceptable for food applications.

In the following examples, parts and percentages are based on 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, a freeze-thaw test was developed here. 12
Water starch 575f (anhydrous and 3f) 150m! ! to make a starch sol by mixing with distilled water. This starch slurry can be heated to [LIN Hot or IN
Adjust the pH to 5.0~&OK% with NaOH and add two parts of McCormick red food coloring to it. This slurry was heated in a boiling water bath with stirring for 20 minutes until the starch granules swelled.
Simmer for a minute. The starch sol thus obtained is placed in a 2 ounce jar, capped and placed in a freezer at below 0 (-18°C) for approximately 66 hours.

The sol was electrolytically thawed (6 hours), tested, and refrozen for the second cycle (18 hours). Repeat the freezing period (18 hours) and thawing period (6 hours) for the third, fourth and fifth cycles. The 6th cycle takes a 66 hour freezing period and the 7th to 10th cycles require an 18 hour freezing period.

The test determines whether the water separates and a gel forms, or no gel forms yet but the sol becomes opaque and pink in color, or the viscosity and/or texture changes significantly (e.g. low viscosity and rough texture). 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 a control is tested for each sample.

Example 1 This example illustrates the better low temperature stability of the natural and derivatized starch of the present invention compared to the natural and derivatized Wakinimaise starch.

By wet milling one of the given starch sources, Table 1
The starch shown in is obtained. The low temperature stability of each starch was evaluated using the procedure described above, and the results are shown in Table 1.

Table 1 Natural waxy maize C vs. 111) 1 Waxy maize 0 derivatized with 5-thiacetic anhydride (comparative example) 1 Derivatized with 5-thiacetic anhydride and 0.12% adipic acid-
Waxy maize 0 crosslinked with acetic anhydride (comparative example)
1 Waxy maize derivatized with 50% propylene oxide and cross-linked with α02 phosphorus oxychloride) 41 (comparative example) 1 Derivatized with 5.0% propylene oxide, 002
Waxy maize cross-linked with phosphorous oxychloride (comparative example) 2 Derivatized with 7.5% propylene oxide, 0.
021 Waxy maize cross-linked with phosphorus oxychloride (
Comparative example) 7 Waxy maize crosslinked with α4%sTMp 1C10
3 Natural wxsu2A in embryo plasma 6Custom
Farm Eieed Co11ection-C!
Natural'@X8u2mu3 in embryonic plasma in F118 0Natural wxsu2B5Cu in H45 embryonic plasma
stom Farm Eleed 0ollectio
Native wxeu2B in embryonic plasma in n-OFS a
6 natural wxeu in 0H45 embryo plasma 4 natural wxeu in transient mutant H7 embryo plasma 7 rL4%v in STMP-crosslinked 0H45 embryo plasma
wxsu2A9Cus in transient mutant B37 embryo plasma derivatized with ncsu2B35-thiadiacetic anhydride and cross-linked with α12thiadivic acid-acetic anhydride.
tom Farm 5eed 0ollection-
wxsu 2 A in embryonic plasma in OFBB and AO
A 50:50 mixture with wxsu2A in the transient OH7 embryo plasma derivatized with 0.0% propylene oxide and cross-linked with phosphorus oxychloride. Indicates a source different from the source obtained.

＋L 脣 These samples, which normally exhibit improved freeze-thaw stability compared to natural waxy images, are not subject to the rigorous testing of the present invention, as this test measures only the difference in low-temperature stability. Therefore, it shows no difference.

From these results, the natural starch sol of the present invention exhibits better freeze-thaw properties than the natural waxy maize starch sol and even than the acetylated waxy maize starch sol. In addition, test 'X pull-kai fJaapcrv-2
It is clear that all of the two sources of adhesion give excellent starch (P powder thickener) t-freeze-thaw properties.

Further, the cross-linked starch of the present invention has superior low-temperature stability to that of cross-linked waxy maize, and the cross-linked and derivatized starch of the present invention has superior low-temperature stability to that of cross-linked waxy maize that is derivatized to the same degree. It turns out to be much more stable at lower temperatures.

In fact, the cross-linked derivatized starches of the present invention have the same or better low temperature stability than the more highly derivatized cross-linked waxy maize. Also, the underivatized cross-linked starch of the present invention has the same or better low temperature stability as cross-linked waxy maize derivatized with propylene oxide at 5% t. 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 wzsu 2 A in modified oH7 embryo plasma was
Stir in H and low pH salt aqueous solution. A flavor test was conducted on the resulting starch slurry and it was found that the starch did not adversely affect the flavor of the slurry at either high or low pH.

Example 3 Two cherry-bai fillings are made using the same ingredients and t except that the starch is a waxy gugary of the present invention cross-linked with Q, 014 phosphorus oxychloride to the dipping starch.
-2 mutant starch is used, the other is waxy maize derivatized with 5-thiacetic anhydride and not cross-linked with [112% adipic acid-acetic anhydride] for comparison. , 10
When subjected to more than one freeze-thaw cycle (each cycle consists of one
Cherry-baby stuffing was made using derivatized waxy starch using natural mazy sugar-2 mutant starch (including freezing overnight at 7°C (-A3C) and then thawing for 6-7 hours). It is more stable than other pie fillings. 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 bulbs from the juice. The starch of Example 2 was slurried in the tomato juice thus obtained (1.8 weight tons based on the total sauce weight).
amount of chi).

The resulting slurry is thickened until thickening (C thickening) occurs. Then add the tomato pulp and seasonings and continue kneading until the desired consistency of consistency 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, the following ingredients are thoroughly mixed and the mixture +1i-190”FC818
Heat to ℃).

Beef broth 62.6 g Water 24.5 g Starch of Example 2 30 g Flour 2.0 g Salt 14 g Sodium glutamate α4% Spices 1.29 g Melted vegetable shortening 5. Add 1% slowly and reduce to 19°~195° (81°
8-906°C) for 8 minutes. If desired, add brown dye to the gravy, pack the gravy into containers, and freeze.

The resulting brown GuV-Vee was found to be stable upon repeated freezing and thawing cycles.

In making frozen pudding (butterscotch), the following ingredients are mixed thoroughly.

Starch of Example 2 19. Oti sugar 4 [10% Maltodextrin 2 [LO% Non-fat dry milk solids 2 [11%] Salt α9 butter Scotch flavoring Appropriate amount Add a portion of the above mixture to 22.55% 47. b s T
.

of water and 3 (100% cream substitute).

185-190 (85-87) while stirring well.
．． 8° C.) and keep at this temperature for 10-15 minutes. Pour 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 cold-stable compared to that obtained using chemically stabilized waxy starch. This thickener composition can also be used in addition to food applications, such as binding,
It can be used in pastes or adhesives, preferably as a thickener or stabilizer for various food products.

Agent Hikaru Esaki Agent: Hikaru Esaki

Claims (1)

[Claims] 1. A thickened cold sol comprising an effective amount of waxy starch and water from plants of the wxsu2 genotype, its transpositions, inversions, mutations and mutations, and at least one food product. In food products, foods made using the above sol are
A food product characterized in that it is able to withstand at least one freeze-thaw cycle better than a sol of natural waxy starch from a corresponding plant that is not of the wxsu2 genotype. The food according to claim 1, wherein the λ starch is Wakinimayzu starch. (v) The food according to claim 2, wherein the starch is natural (non-gelatinized) starch. Higashi The food according to claim 2, wherein the starch is crosslinked. 5. The starch is selected from the group consisting of epichlorohydrin, linear dicarboxylic acid anhydrides, acrolein, phosphorous oxychloride, and tritutaphosphate, and the crosslinking agent is crosslinked using a conceptual crosslinking agent in an amount of at least 1 weight of LOO based on the weight of starch. The food according to claim 4. & The food according to claim 2, wherein the starch is derivatized and contains a substituent. 1. Starch is derivatized with suitable reagents to give hydroxypropyl ether, phosphate, octenyl succinate, acetate or tertiary or quaternary amine ether derivatives. food. (a) The food according to claim 2, wherein the food is pie filling, tomato sauce, gravy or pudding.