WO2021086273A2

WO2021086273A2 - Modified-acetylated distarch adipate and products containing thereof

Info

Publication number: WO2021086273A2
Application number: PCT/TH2020/000073
Authority: WO
Inventors: Waesarat SOONTORNCHAIBOON; Panchasorn SUKKASEM; Nutthawee THAMJEDSADA; Chutarat KOWITTAYA; Pitipong WANAKHACHORNKRAI; Suchitra WONGPRAYOON
Original assignee: Sms Corporation Co., Ltd.; Siam Quality Starch Co., Ltd.
Priority date: 2019-10-29
Filing date: 2020-10-28
Publication date: 2021-05-06
Also published as: WO2021086273A3; CN114651015A; CN114651015B

Abstract

The present invention provides an improved production method of cross-linking modified acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat by adjusting the conditions and preparation processes suitable for use as an adhesion agent in deep-fried food products and as a meat binder in processed meat products without the presence of acetaldehyde and phosphorus in the products. Acetylated distarch adipate from tapioca starch is prepared at a pH value of 8- 8.5 and the temperature in the range of 25-30 °C by dropping a mixture of adipic acid 0.25%-0.375% (w/w, on a dry starch basis) and acetic anhyd ride 2.52%-7.56% (w/w, on a dry starch basis) into the prepared starch suspension. Then, a treatment of the obtained acetylated distarch adipate is performed with a mixture of sunflower oil 0.25% (w/w, on a dry starch basis) and emulsifier 0.1% (w/w, on a dry starch basis) in order to obtain oil treated acetylated distarch adipate. Then, a treatment of the obtained oil treated-acetylated distarch adipate is performed by adding sodium hypochlorite at a pH value of 4. 5 and temperature of 37 °C. Then, stirring for 60 minutes to enhance an oil storage on starch molecules through covalent bonds to obtain the oil and sodium hypo chlorite treated-acetylated distarch adipate. Then, a heat treatment of the obtained oil and sodium hypochl orite treated-acetylated distarch adipate is performed at 130 °C for 30 minutes to obtain a cross-linking modified-acety lated distarch adipate inhibited by oil, sodium hypochlorite and heat with an adhesion ability when is used as pre-dust or to improve the stability of viscosity when is used as batter slurry. It also has an excellent binding property when is used as a meat binder in processed meat products.

Description

MODIFIED-ACETYLATED DISTARCH ADIPATE AND PRODUCTS CONTAINING

THEREOF

TECHINCAL FILED Food chemistry relating to the preparation process of modified-acetylated distarch adipate and products containing thereof.

BACKGROUND ART

Deep-fried battered and breaded foods are very popular nowadays. These products can be cooked in household by providing commercially available starch-based coatings and applying them on foods such as meat, vegetables or fruits, etc. The desired properties of starch-based coating products are, such as available proper viscosity, good ability to adhere to the food surface, or compatibility with free water in meat and frying oil to prevent the coatings blow-off during frying including reduce oil uptake and preserve the crispiness. The production of deep-fried battered and breaded products in the industrial scale are typically coated with three layers of starch-based coatings, i.e., “predust”, which is used for a direct coating on food pieces as the first dry coating layer to improve an adhesion between the food surface and the subsequent coating layers; “batter”, which is used in the form of thickening batter slurry and applied for the second coating layer; and “breader”, which is used as a dry coating outer the food surface to increase the food texture and the crispiness of the product. Initially, the problem is often attributable to the wrong use of coatings, i.e., using of a predust for both of dry coating and/or wet coating slurry. This causes the said slurry lacking the viscosity property when it was dissolved in the cold water, thereby affecting to the ability of the predust to adhere the food surface. In addition, it also lacks of the crispiness property after being fried as the starch absorbs water and swells excessively when heated, which subsequently results in oil uptake after frying. For this reason, the manufacturers have attempted to develop the predust in which giving a proper adhesion between the food pieces and the other coating layers, performing the viscosity when dissolved in cold water and/or when heated, and do not absorb water and swell in excessively in order to reduce the coatings blow-off and oil uptake of deep-fried food products after frying. There are enhancements in the adhesion ability of starch-based coatings through the process of native starch modification (according to the industrial standard of the manufacturing process of starch, the term “starch” refers to a high purity starch, due to the removal of most impurities, such as proteins, fats and minerals, remaining the component of carbohydrate mainly which composed of carbon, hydrogen and oxygen (Sriroth, K. and K. Piyajomkwan. 2003. Starch Technology. 3^rd edition. Kasetsart University Press, Bangkok, page 1 )) by using physical or chemical modification methods which disclosed in the related prior art or other examples, such as by performing pregelatinization of starch in order to provide a cold water swelling property to starch which enhances them a better adhesion to the food surface before being fried; by processing oxidation with chlorine compounds; by cross- linking modification to reduce the swelling power of starch granules. (Niyomvit, N. and A. Uthaipatanacheep. 1985. Cooking Science. Kasetsart University Press, Bangkok, pages 1 17-161 ) or by cross-linking modification in combined with substituting functional group on starch molecules through esterification or etherification process to have a better adhesion of the starch during frying and thereby reducing oil uptake of starch- based coating during frying, and then more crispiness.

Alternatively, WO2012111199 disclosed the use of modified starch in the group of starch acetate (E1420) which is specifically only produced from vinyl acetate monomer (VAM) for use as a food-coating material in which having a good adhesion property to the food surface. It mentioned on an adjustment of pH to be in acidic after finishing the esterification reaction. However, the obtained final products have the same property as those in the cross-linking modified starch, i.e., its breakdown viscosity value was lower than 200 BU. A person skilled in the art of starch modification can understand that this appearance is subjected to acetaldehyde which is a byproduct of this reaction, are linked together with starch molecules under the acidity as shown in the figure. This makes a possibility of residual of acetaldehyde in the starch molecules as a part of an acetal bond arising from the cross-linking reaction.

Starch + Vinylacetate starch + Acetoealato aldehyde

Acetaldehyde is a substance that can be toxic to the cells if received in large quantities and/or continuously received. It can induce cancer in various organs that have been exposed to this substance. At present, in Canada, vinyl acetate monomer does not identified as an approved chemical substance to modify food starch (Government of Canada. 2016. List of Permitted Starch- Modifying Agents (Lists of Permitted Food Additives)Document Reference Number:NOM/ADM- 0074; NOM/ADM -0048; NOM/ADM -0037). As a result of all mentioned above, there are efforts to develop products that meet consumer’s requirements of which significantly emphasize on health along with safety and are becoming very popular nowadays.

Tian et al. (Tian, S., Y. Chen, Z. Chen, Y. Yang and Y. Wang. 2018. Preparation and characteristics of starch esters and its effects on dough physicochemical properties. Journal of Food Quality. 1-7) including Ackar et al. ( Ackar, d. , J. Babic, A. Jozinovic, B. Milicevic, S. Jokic, R. Milicevic, M. Rajic and D. Subaric. 2015. Starch modification by organic acids and their derivatives: A review. Molecules. 20: 19554:19570.) reviewed research studies relating to the modification of starch with organic acids, that described a modification of starch with a mixture of acetic anhydride and adipic acid in an alkaline aqueous suspension by cross-linking reaction and an esterification as follows:

From the reaction shown above, acetylated distarch adipate is obtained as a main product (El 422; starch acetate hexanedioate). The optimum condition required for the production of the tapioca starch based-acetylated distarch adipate is adipic acid 0.050% (w/w, on a dry starch basis), acetic anhydride 3% (w/w, on a dry starch basis), at pH 8.0 for 90 minutes. The properties of the acetylated distarch adipate are resistant to the shear force and acid, high thermal stability, and providing a viscosity when dissolved in cold water. In addition, further studies on the retrogradation of the potato starch based-acetylated distarch adipate showed the increase in retardation to the retrogradation of paste including decrease in the esterification and paste viscosity. Moreover, the resistant to the amyloglucosidase digestion of this modified starch can be made them possibly use as ¾-type resistant starch (Kapelko-Zeberska, M., T. Zieba, R. Spychaj and A. Gryszkin. 2015. Acetylated adipate of retrograded starch as RS 3/4 type resistant starch. Food Chemistry. 188: 365-369). In 2017, the European Commission conducted a safety assessment to the use of modified starches including acetylated distarch adipate as food additive in various types of food. The result showed that El 422 can be used in various types of food (exception in infant and children foods). It can be consumed in the right amount and do not toxic to any organ when testing in rats and hamsters, except only for a weight gained in cecum and a greater accumulation of calcium (EFSA Panel on Food Additives and Nutrient Sources added to Food (ANS), EFSA Journal, updated 31 October 2017; doi; 10.2903/j.efsa.2017.4911).

From all the reasons mentioned above, the acetylated distarch adipate is thus used in food industry that requiring paste viscosity stability, suitable for acidic food and high heat processing and able to keep in cooling condition by providing a viscosity along the time of retention, such as soups, sauces, salad dressings, pie fillings, infant food. Additionally, it is also used as an additive for better adhesion in battered and breaded products (Imeson, A. 1992. Thickening and gelling agents for food. Blackie Academic and Professional, Bishopbriggs., Glasgow. 258p). The use of the acetylated distarch adipate, including modified starches in the group of acetylated distarch phosphate ( E1414) in battered products has been disclosed in Japanese Application No. JP2012235752A.

Although starch in cross-linking modified group based on phosphate chemical substance in the phosphorus-containing group, such as E 1412; distarch phosphate, El 414; acetylated distarch phosphate, El 442; hydroxypropyl distarch phosphate, is qualified suitably for a variety of food that requiring paste viscosity stability, including being food-coatings. However, the phosphate in the above cross-linking starch structure may be more sensitive to chronic kidney patients who must limit an intake of phosphate from food than normal people (The Nephrology Society of Thailand. 2015. Recommendations for Monitoring Chronic Kidney Patients before Renal Replacement Therapy 2015). This causes a limitation to the selection of these modified starches for food consumption in some consumer groups. For this reason, the cross-linking modified starch in combination with acetylation in the group of acetylated distarch adipate is used as an initial starch for subsequent steps of modification under this invention. However, there are also problems on the paste viscosity stability of said starch slurry that renders unstable viscosity, which effects an ability of food surface adhesion including the problem of the said starch-based coating blow-off from food pieces due to the excessive water absorption and swelling when the acetylated distarch adipate is used.

An additional method of enhancing an adhesion between starch and meat that is used to the production of food-coating material is oil/fat treatment in combination with heat treatment. This allows the inhibition or the limitation of starch to swell excessively due to the forming of a cross-linking bond between starch and starch and/or starch and amino group from the meat. Strengthening the said bond will improve the adhesion as well as reduce an excessive swelling of starch. Moreover, the presence of oil/fat on starch molecules resulting from an enhanced ability on the reaction between the starch and oil/fat by adding emulsifier can also reinforce the features of final products in terms of reducing oil uptake after frying.

JP2012165724A (‘724) discloses the production of batter used for a deep-frying which giving a crispy texture and juicy taste by treating oil/fat to the resulting acetylated starch obtained from the acetylation reaction between tapioca starch and vinyl acetate. A proper concentration of a mixture between oil/ fat and emulsifier is in the range of 0.02- 0.5% by weight of a dry starch. Oil and fat are selected from safflower oil, grape seed oil, soybean oil, sunflower oil, rapeseed oil, peanut oil, olive oil, palm oil, coconut oil, beef fat, pig fat, chicken oil, fish oil, and fractionated oil, etc. The emulsifier is selected from glycerin esters of fatty acids, sorbitan esters of fatty acids, sucrose esters of fatty acids, and lecithin, etc. It is also possible to perform other treatments, such as a combination of physical treatments, including bleaching treatment, acid treatment, alkali treatment, and heat treatment, etc.

The publication of US Patent Application No. US20100055293A ( ‘293) discloses a method for reducing oil uptake in deep-fried foods by replacing some cook- up starch and/or instant starch in food ingredients with hydrophobic starch. It is revealed that the oil uptaking of the resulting products have remarkable lower up to 30% . The said hydrophobic starch can be prepared by adding hydrophobic group on starch molecules through ether bond, ester bond or amide bond, etc. For example, octenyl succinate starch is prepared, then the molecular size is decreased through acid or enzyme digestion before replacing the partial amount of the said starch in food. JP2012235752A (‘752) discloses the use of esterified starch including acetylated distarch adipate from tapioca starch as a dry coating starch in the Tatsuta fried foods, which the food is marinated in sauce and coated with starch before frying. Its appearance after frying is different from an appearance of other deep-fried food, that giving the fluffy white flakes on the surface of food pieces. There are broadly mentioned that further treatments might be performed, such as oil/fat/emulsifier treatment, heat treatment or acid/alkali/enzyme treatment, etc., in combination with esterification without impairing the resulting effects of the invention disclosed in ‘ 752, including the tapioca starch based-acetylated distarch adipate prepared from 40% (w/w) of starch suspension, the pH in range of 7 - 10 , adipic acid 0.005 to 0.05% (w/w, on a dry starch basis) and acetic anhydride 0.5 to 6% (w/w, on a dry starch basis). In addition, it also discloses the applying of fat/oil at 2-8% by mass in the Tatsuta frying flour. Fat/oil are selected from linseed oil, safflower oil, grape seed oil, soybean oil, sunflower oil, com oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, olive oil, palm oil, coconut oil, beef fat, pork fat, chicken fat, fish oil, and fractionated oil, etc.

However, although the above preparations of the modified-acetylated distarch adipate have been disclosed, it is just broad modification methods without specifying details of substances, amounts, methods or steps for additional modification, including the features obtained from the modification. Only the type and amount of the modifying substances are specified to obtain acetylated distarch adipate having a specific viscosity for use as pre-dust with the Tatsuta fried food. It, therefore, can be said that there is still required to produce modified-acetylated distarch adipate that can be used in a wider variety of products, including for use as an auxiliary agent of meat binder in processed meat products such as ham, surimi, artificial squids, crab sticks or fish tofu, etc.

DISCLOSURE

The present invention is related to the production of modified-acetylated distarch adipate for use as an adhesion agent in deep fried food products and as a meat binder in processed meat products without the presence of acetaldehyde and phosphorus therein. The objective of this invention is to enhance an ability of food surface adhesion when used as a pre-dust and/or batter, including a meat binder in processed meat products, and to improve viscosity stability when used as thickening batter slurry before coating and deep-frying in the following four main production processes:

1) Preparation of acetylated distarch adipate in an alkaline state at room temperature.

2) Treatment of the prepared acetylated distarch adipate with a mixture of specific oil and emulsifier to obtain an oil treated-acetylated distarch adipate.

3) Treatment of the obtained oil treated-acetylated distarch adipate by adding sodium hypochlorite (NaOCl) in an acidic state to obtain an oil and sodium hypochlorite treated- acetylated distarch adipate.

4) Heat treatment of the obtained oil and sodium hypochlorite treated-acetylated distarch adipate to obtain a cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat. Patent applicants had performed numerous experiments to obtain suitable conditions for producing the above modified-acetylated distarch adipate. As a result, they succeed to have the first embodiment of the invention relating to the production method of the modified-acetylated distarch adipate enabling condition adaption suitable for deep fried food products and for use as a meat binder in meat processed food products according to the following steps:

Preparation of an acetylated distarch adipate from tapioca starch in an alkaline state at pH of 8-8.5 and the temperature of 25-30 °C by dropping a mixture of adipic acid 0.125%-0.375% (w/w, on a dry starch basis) and acetic anhydride 2.52%-7.56% (w/w, on a dry starch basis) into the prepared tapioca starch suspension; - Treatment of the obtained acetylated distarch adipate with a mixture of sunflower oil

0.25% (w/w, on a dry starch basis) and emulsifier 0.1% (w/w, on a dry starch basis) to obtain an oil treated-acetylated distarch adipate;

Treatment of the obtained oil treated-acetylated distarch adipate by adding sodium hypochlorite (NaOCl) in an acidic state at pH of 3.5-5.5 and the temperature of 35-40 °C, and then stirring for 60-90 minutes to obtain an oil and sodium hypochlorite treated-acetylated distarch adipate; and

Heat treatment of the obtained oil and sodium hypochlorite treated-acetylated distarch adipate at the temperature of 130-150 °C for 30-60 minutes to obtain a cross-linking modified- acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat. In addition, the second embodiment of the invention is the modified-acetylated distarch adipate obtained from the method of the first embodiment for use in starch based-coating products without being limited to the pre-dust and batter.

The third embodiment of the invention is deep-fried food products that having starch based- coating products comprising of the modified-acetylated distarch adipate obtained from the method of the first embodiment above. The deep-fried food products made from the said starch based- coating products have a viscosity stability and a good adhesion between coating layer and food pieces as will be described hereinafter in the examples of the experiments.

The fourth embodiment of the invention is processed meat products, such as ham, surimi, artificial squids, crab sticks or fish tofu that having starch based-coating products which is consisting of the modified-acetylated distarch adipate obtained from the method of the first embodiment above. The processed products from such meat have been improved its binder property between meat to be processed due to an enhancement of adhesion between meat by using the said starch with the same basis as that of the deep-fried food products in the third embodiment as will be described hereinafter in the examples of the experiments.

DESCRIPTION OF DRAWINGS Fig.1 is a graph showing the viscosity in water of modified-acetylated distarch adipate after conducting an analysis with the Brabender Visco-Amylograph at 6% (w/w) of starch suspension.

DETAIL OF INVENTION

Hereinafter will be described the details of the production method of modified-acetylated distarch adipate in various stages. Those who have a skilled in the art of starch modification should understand that the details described herein are not limited to only a single number or a process or a type of substance, but the scope of this invention must also include any equivalents or modifications or practicability the person skilled in this field can foresee. For this reason, the followings are merely an additional detailed explanation regarding the method of this invention, the resulting product and the benefits that should be obtained from such method.

According to one example of the first embodiment of the invention, although it is not limited to any specific type of starch to be used in the production of modified-acetylated distarch adipate, tapioca starch is the most suitable for this invention.

According to another example of the first embodiment of the invention, it is provided preparation of acetylated distarch adipate from tapioca starch at 35-40% (w/w) of tapioca starch suspension.

According to another example of the first embodiment, it is provided preparation of acetylated distarch adipate in an alkaline state by gradually adding a mixture of adipic acid 0.125%-0.375% (w/w, on a dry starch basis) and acetic anhydride 2.52%-7.56% (w/w, on a dry starch basis) at pH in the range of 8-8.5 and the temperature of 25-30 °C. After adding all such acid mixture, stirring it for 15 minutes.

According to another example of the first embodiment of the invention, it is to perform treatment of the prepared modified-acetylated distarch adipate with a mixture of sunflower oil 0.25% (w/w, on a dry starch basis) and emulsifier 0.1 % (w/w, on a dry starch basis), wherein the suitable emulsifier in this invention is sucrose palmitate at HLB of 15 (such as RYOTO™ SUGAR ESTER P-1570 produced by Mitsubishi-Chemical Foods Corporation).

According to another additional example, it may obtain a mixture of sunflower oil and emulsifier by way of conventional methods. For example, mixing sunflower oil and emulsifier in the amount specified above in water approximately nine times of the total weight of the sunflower oil and emulsifier. Then, stirring at 68 °C for 4 hours. The mixture of the sunflower oil and emulsifier is obtained as desired. A droplet size of the mixture may be suitably determined for performing treatment of the acetylated distarch adipate. For instance, the droplet size of the mixture is in any range of less than 100 microns, etc.

According to another additional example, prior to the treatment of the acetylated distarch adipate with the mixture of sunflower oil and emulsifier, the conditions may be adjusted until the pH value is reached in the range of 3.5-5.5 and the temperature is in the range of 35-40 °C, so as to discontinue the reaction of the acetylated distarch adipate. According to another additional example, the oil treated-acetylated distarch adipate may be added with sodium hypochlorite in optimum conditions such as 500-2, 000 ppm at pH in the range of 3.5-5.5 and the temperature is in the range of 35-40 °C to enhance an ability to maintain the oil on starch molecules and hydrophobic property through covalent bonds. The selection of the content of sodium hypochlorite in this specific pH condition will resulted in a different reaction from conventional one. For example, in case of bleaching starches with sodium hypochlorite, it is usually made in an alkaline state and uses low sodium hypochlorite content (< 500 ppm), or in case of the production of oxidized starch, it is usually made in an alkaline state and uses high sodium hypochlorite content (>2,000 ppm).

According to another additional example, the obtained oil and sodium hypochlorite treated- acetylated distarch adipate may be washed and/or dried in order to obtain a suitable form of such starch prior to heat treatment, especially, the dried acetylated distarch adipate. However, the specific condition for washing and/or drying are not specified, as long as the washed and/or dried acetylated distarch adipate does not loss its properties of this invention due to such washing and or drying. In an example that is not limited to, the above drying method may be a drying with a flash dryer. As an additional unrestricted sample, the condition for starch drying is to dry the starch with a flash dryer at 100 °C for 20 minutes, etc.

According to another additional example, the treatment of the oil and sodium hypochlorite treated-acetylated distarch adipate which is performed by washing and drying as stated above with heat at the temperature in the range of 130-150 °C for a suitable time, e.g. 30 minutes, in order to obtain the cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat under this invention. In another specific example, before oil treatment and heat treatment, the pH value may be adjusted suitably for such treatments, in particular in the range of 5.5-6.5 and the most suitable pH value is 6.

Hereinafter is a description of the production and use of starches under this invention. It is merely an illustration that does not limit to the scope of this invention.

Examples

Experiment 1 ; Production of Acetylated Distarch Adipate

To prepare samples of acetylated distarch adipate under this invention by using the proportions of adipic acid and acetic anhydride to obtain an expected Degree of Substitution of acetyl group per unit of glucose (DSAC) and a degree of inhibition expressed as an expected viscosity in Brabender unit (BU) as shown in Table 1. It is started the preparation of 40%(w/w) of tapioca starch suspension, then adjusted a pH value to be in the range of 8-8.5 at the temperature in the range of 25-30 °C. Then, adding a mixture of adipic acid and acetic anhydride at the concentration shown in Table 1. Stirring continuously for 15 minutes together with controlling the pH value to be constantly in the range of 8-8.5 during such 15 minutes stirring. Then, adjusting the pH value to 6.0 before performing subsequent step of modification. Actual viscosity values are measured and obtained by a Brabender Visco-Amylograph (BRABENDER Viscograph-E, Germany) at 6% (w/w) of starch suspension, with a total volume of 500 grams, as shown in Table 2.

Table 1: Samples of acetylated distarch adipate obtained from various volumes of the concentration of adipic acid and acetic anhydride. DSAC value and inhibiting level shown as expected viscosity in the Brabender Unit (BU).

Expeiment2: Preparation of Modified- Acetylated Distarch Adipate To prepare samples of modified-acetylated distarch adipate under this invention by obtaining the acetylated distarch adipate in Experiment 1 first, then adjusting a pH value to 4.5 and increasing the temperature to 37 °C, followed by treatment of all samples of the obtained acetylated distarch adipate with a mixture of sunflower oil 0.25% (w/w, on a dry starch basis) and emulsifier (RYOTO™ SUGAR ESTER P-1570 produced by Mitsubishi-Chemical Foods Corporation) 0.1% (w/w, on a dry starch basis). Then, performing treatment of the acetylated distarch adipate that has been modified with the oil stated above with sodium hypochlorite for 500- 2,000 ppm at pH of 4.5 and temperature in the range of 35-40 °C for 60 minutes. Then, the reaction is discontinued by adjusting the pH value to 6.0, and followed by washing and drying all prepared samples with the Flash dryer at 100 °C for 20-30 minutes, and then performing heat treatment to the obtained acetylated distarch adipate modified with oil and sodium hypochlorite at 130-150 °C for 30 minutes. A cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat is obtained. Then, actual viscosity values are measured and obtained by a Brabender Visco-Amylograph (BRABENDER Viscograph-E, Germany) at 6% (w/w) of starch suspension, with the total volume of 500 grams. Actual DSAC values are also measured by the standard method, JECFA Monograph 19, by first stirring the 17% (w/w) of starch suspension with the total volume of 1 8 grams, for 1 0 minutes. Then, adding 25 ml of a 0. 1 normal concentration of sodium hydroxide solution (NaOH), the container is closed and continuously stirring for 50 minutes. The solution is then titrated with a 0. 1 normal of sulfuric acid solution (H2SO4) until the solution is turned into white opaque. Recording the volumes of sulfuric acid solution and calculate for DSA_C according to the following formula:

DS_AC = G0.1 N NaOH x 25 mil - G0.1 N H?SCk x V srn 1 / 1000 Dried Starch Weight /162

Wherein VH2S04 is the volume of consumed sulfuric acid The results are shown in Table 2 and Fig.l . Table 2: Expected and actual DSAP. expected and actual viscosity of cross- linking acetylated distarch adipate before and after oil. NaOCl and heat modification.

Experiment 3: Determination of Viscosity Stability of Starch Suspension To examine viscosity stability of starch suspension under this invention by way of comparing with another batter starch available in the market (S-TEX SP of SMS Corporation) by dissolving the cross- linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat under this invention and the S-TEX SP which has been kept at room temperature for 0, 30 and 60 days and at the condition of accelerated the loss of stability at temperature of 70 °C for 5 hours, with cold water. Preparing 35% (w/w) of starch suspension, with the total volume of 200 grams, then stirring at a speed of 250 rpm for 1 minute, and then measuring viscosity by a Brookfield, LV DV2T model, USA ( AMETEK Brookfield) . The viscosity unit is in centipoise and the results are shown in Table 3.

Table 3: Viscosity of starch solution kept in various temperatures and times

From Table 3, it is evident that the starch sample under this invention has a better viscosity stabilization property when compared to the S-TEX SP. While the S-TEX SP has an enhanced viscosity based on storage time period, but the starch under this invention does not have any impact from such storage either at the normal temperature or at the condition of accelerated the loss of stability.

Experiment 4 : Preparation of Deep-fried Food Products Containing Modified- Acetylated Distarch Adipate To prepare deep-fried food products for conducting a test of starch adhesion ability under the present invention by using it as pre-dust by dry coating of meat with all samples of the obtained cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat in Experiment 2 and the comparison sample, S-TEX SP (SMS Corporation), and the sample from AMSCO which is used as pre-dust (Sample 10). Then, coating the pre-dusted meat with batter slurry as the second coating layer, wherein such slurry is comprising of 77.28% of wheat flour, 20% of batter made by SMS Corporation, 1% of sodium pyrophosphate acid, 0.72% of sodium bicarbonate, and 1% of salt, and then final coating with breadcrumbs. Thereafter, frying them in vegetable oil in deep fryer (Auto lift-up electric fryer, WTFL-6L-C10) at 170-180 °C for

3 minutes. Then, the obtained deep-fried food samples are performed a sensory evaluation based on Experiment 5.

Experiment 5: Sensory Evaluation

To evaluate sensory of the deep-fried products obtained from Experiment 4 by 5 panelists (n=5) using the rating test method with 5 points hedonic scale. The evaluation is conducted in the same area and in the same condition. Score criteria of the sensory evaluation are shown in Table

4 and the results are shown in Table 5. Table 4: Score Criteria of Sensory Evaluation

Table 5: Results of Sensory Evaluation of Deep-fried Products

It can be seen from Table 5 that the modified-acetylated distarch adipate prepared from tapioca starch in Sample Nos. 1-6 as an adhesion agent in the deep fried food products have good sensory evaluation results as that of the commercial pre-dust in Sample No. 10 and better results than that of the S-TEX SP in all criteria. On the other hand, Sample Nos. 7-9, that have the highest expected viscosity (900 BU), which obtained from low concentration of adipic acid (0.125% by dried starch weight), have worse results than those of the 2 comparison samples in all criteria. For this reason, it can be concluded that the production condition of this invention described above is used at least 0.250%-0.375% (w/w, on a dry starch basis) of adipic acid and 2.52%-7.56% (w/w, on a dry starch basis) of acetic anhydride in order to obtain the sensory properties as desired.

Experiment 6; Preparation of Processed Meat Products in the Category of Ham.

To prepare processed meat products for testing an ability of the starch under this invention as a meat binder for ham products in order to substitute transglutamines (TG) and carrageenan (CG) which are commonly used as a meat binder, by using the cross-linking modified acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat (Sample No. 5) which was obtained from Experiment 2 as a meat binder and is compared to the normal TG and CG and the comparison sample of the acetylated distarch adipate derived from tapioca starch without oil, sodium hypochlorite and heat treatments (Sample No.11), including a control sample that having no binder. The preparation process starts with preparing 400 grams of coarsely ground meat (approximately temperature of meat around 12- 14°C), weighing the ingredients according to the proportions shown in Table 6, mixing all ingredients well before marinating for a period of time (30 minutes marinate, 5 minutes stop, continuous marinate for another 30 minutes) . After that, curing it at 4 °C for 18 hours, followed by compressing all the ingredients into a container. Then, steaming at 80 °C for 90 minutes and then cooling it immediately and keeping at 4 °C.

Table 6: Ingredients of Processed Meat Products in the category of Ham

Performed an appearance assessment of the obtained ham by 15 panelists ( n= 15) , testing and score criteria are shown as follows:

Testing Criteria 1) Percentage of Cooking Yield = (Weight of ham after steam / weight of ham after marinade) x 100

2) Manually testing of binding property

3) Testing of slice ability into thin pieces

4) Testing of ham firmness Score Criteria for Topics 2) - 4)

Extremely low = 0, Very low = 1, Low = 2, Moderate = 3, High = 4, Extremely high= 5 Test results are shown in Table 7.

Table 7: Test Results of Processed Meat Products in the category of Ham

Based on Table 7, it showed that hams made with the modified starches under this invention have superior product evaluation results over other samples in all testing criteria. It is thus obvious that the modified starch under this invention is not only capable for use with deep- fried food products, but is also capable for use with processed meat products in the category of ham as well.

BEST MODE

As described in the detail of invention.

Claims

CLAIMS fClaim 11

Method of producing a cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat, comprising the following steps: (a) Preparation of acetylated distarch adipate from tapioca starch in an alkaline state at pH of 8-8.5 and temperature of 25-30 °C by dropping a mixture of adipic acid 0.250%-0.375% (w/w, on dry starch basis) and acetic anhydride 2.52%-7.56% (w/w, on dry starch basis) into the prepared tapioca starch suspension;

(b) Treatment of the obtained acetylated distarch adipate with a mixture of sunflower oil 0.25% (w/w, on dry starch basis) and emulsifier 0. 1 %(w/w, on dry starch basis) to obtain oil treated-acetylated distarch adipate;

(c) Treatment of the obtained oil treated-acetylated distarch adipate by adding sodium hypochlorite (NaOCl) in an acidic state at pH of 4.0-5.0 and temperature of 35-40 °C, and then stirring for 60-90 minutes to obtain oil and sodium hypochlorite treated-acetylated distarch adipate; and

(d) Heat treatment of the obtained oil and sodium hypochlorite treated-acetylated distarch adipate at 130 °C for 30 minutes to obtain a cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat.

[Claim 2] Method of producing the modified-acetylated distarch adipate according to Claim 1, wherein the treatment of the obtained acetylated distarch adipate with a mixture of sunflower oil 0.25% (w/w, on dry starch basis) and emulsifier 0.1% (w/w, on dry starch basis), the suitable emulsifier is sucrose palmitate at HLB of 15.

[Claim 3] Method of producing the modified-acetylated distarch adipate according to Claim 1 or

Claim 2, wherein the treatment of the obtained oil treated-acetylated distarch adipate is performed by adding sodium hypochlorite (NaOCl) in an acidic state at pH of 4.3-4.7.

[Claim 4]

Method of producing the modified-acetylated distarch adipate according to Claim 1 or Claim 2, wherein the treatment of the obtained oil treated-acetylated distarch adipate is performed by adding sodium hypochlorite (NaOCl) in an acidic state at pH of 4.5.

[Claim 5] Method of producing the modified-acetylated distarch adipate according to any one of Claims 1 to 4, wherein steps of washing and/or drying the oil and sodium hypochlorite treated- acetylated distarch adipate are additional steps after step (c).

[Claim 6]

Method of producing the modified-acetylated distarch adipate according to any one of Claims 1 to S, wherein the acetylated distarch adipate from tapioca starch is prepared by using 35- 40% (w/w) of tapioca starch suspension.

[Claim 7]

The cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat is obtained from the method in any one of Claims 1 to 6.

[Claim 8]

Deep-fried food products comprising the cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat are obtained from the method in any one of Claims 1 to 6.

[Claim 9]

Processed meat products comprising the cross-linking modified-acetylated distarch adipate inhibited by oil, sodium hypochlorite and heat are obtained from the method in any one of Claims 1 to 6.