JP5033553B2 - Emulsification stabilizer - Google Patents

Description

  The present invention relates to an emulsion stabilizer, and more particularly to an emulsion stabilizer that is prepared from starch and has both an emulsification of fats and oils and an oxidation-inhibiting effect thereof.

  Mixing water and oil suitably and mixing them uniformly is called emulsification, and is used in a wide range of fields such as the food processing industry, machine industry, and sewage treatment. The simplest emulsification method is stirring. However, with time, water and oil meet and separate. Therefore, when water and oil are agitated, fine droplets are physically formed using an appropriate propeller / reaction vessel, homogenizer, etc., and individual particles are dispersed to prevent phase separation between the oil and water. .

  In order to further increase the efficiency of emulsification, an amphiphilic substance such as a surfactant is added as an emulsifier. In food addition applications, it is also used in oil-containing fat products such as mayonnaise, dressing, margarine, butter, and also in doughs containing oil-and-fat products. In particular, various glycerin fatty acid esters, sucrose fatty acid esters and the like are used in food addition applications. In addition, there are many requests to use natural products as much as possible for safety reasons, and saponin, lecithin and gum arabic are also used. However, emulsifiers obtained from natural products tend to be expensive in terms of price. Moreover, it is difficult to say that the quality and production volume are always stable, and it is always affected by price fluctuations.

  Thus, attention has been focused on using starch that is low in price and has a stable supply amount. It is known that starch that has undergone gelatinization or liquefaction forms a complex of oil and fat with the oil and fat when mixed. However, gelatinized or liquefied starch ages with time, destroying the oil-water complex and causing phase separation. In addition, in the case of starch that is only gelatinized, although it exhibits stickiness and adhesion, it becomes a physical hindrance during mixing with fats and oils. As a result, the desired emulsion stabilization performance was not obtained.

  Such problems are addressed by using modified starches to which functional groups such as octenyl succinate esterified starch are added (see Patent Document 1). On the other hand, there is also a restriction on the amount of 1-octenyl succinic anhydride used for starch, which is not perfect.

  In order to assist the emulsifier such as lecithin for the above-mentioned case, stable emulsification performance was obtained by using a starch hydrolyzate in which liquefaction was kept lightly (see Patent Document 2). The starch hydrolyzate of patent document 2 is dextrin in the range of glucose equivalent (DE) 7-30. However, when only dextrin decomposed to an appropriate glucose equivalent is used, desired emulsification performance cannot be obtained. That is, dextrins only aided other emulsifiers.

  Since then, various studies have been conducted on starch modification. For example, there is irradiation of ionizing radiation (γ rays) on starch paste (see Patent Document 3). There is a starch particle in which an enzyme is allowed to act on the starch particles together with a heat treatment to form a hollow, and oil is supported therein (see Patent Document 4). After forming a hollow by the action of an enzyme, there are starch particles which are pulverized and carry an oil (see Patent Document 5).

  In the case of irradiation with ionizing radiation as in Patent Document 3, emulsification of oil and water cannot be obtained although crosslinking acceleration is observed in the obtained starch derivative. Moreover, in the case of the starch particle | grains of patent document 4 and 5, it is restricted to the use with which each particle structure is hold | maintained. For this reason, it is unsuitable when considering extensive food addition while maintaining the emulsified state of oil and water.

As described above, the stabilization of oil and moisture (that is, emulsification of fats and oils) has been studied. On the other hand, since each particle becomes fine during emulsification, the contact surface area between oil and water increases. That is, fats and oils are unavoidable due to the effect of oxidation by oxygen dissolved in moisture. Usually, vitamins such as ascorbic acid, carotene and tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like are used for the purpose of preventing oxidation. Furthermore, there exists a stabilizer which aims at coexistence of emulsification stability and antioxidant (refer patent document 6). The stabilizer of patent document 6 is sugar alcohols, such as a mannitol, and after adding this to oil water, it homogenizes and emulsifies. However, sugar alcohols do not always exhibit sufficient emulsification performance. Accordingly, a material that suitably combines emulsification and fat and oil oxidation prevention has not been obtained.
JP 2005-333949 A JP-A-4-258242 JP 2001-329070 A Japanese Patent No. 3638645 JP-A-10-182701 JP-A-8-259943

  Starch is available at low cost, has excellent storage stability, and is well known in terms of safety. Therefore, the inventors have been convinced that there is room for improvement based on the knowledge of the background art described above, and have continued to intensively study focusing on starch. Then, the inventors discovered that an appropriate dispersion of starch gelatinized product accompanied by ultrasonic irradiation is very excellent in emulsifying action in oil and water. Furthermore, it has also been found that the dispersion is good for suppressing oxidative degradation of fats and oils.

  The present invention has been made in view of the above points, and is based on starch that has been established as a food safety and can be procured easily, exhibits good emulsification stability and can be used for a wide range of addition purposes. Provided is an emulsion stabilizer derived from starch that can also exert an effect of inhibiting oxidation of fats and oils.

That is, the invention of claim 1 is an emulsification stabilizer for an oil-and-fat-containing composition, wherein raw material starch is dissolved and gelatinized, and this is irradiated with ultrasonic waves to give a number average molecular weight (M _n ) of 40 × 10 ⁴ to The present invention relates to an emulsion stabilizer comprising a starch dispersion of 94 × 10 ⁴ .

  The invention according to claim 2 relates to the emulsion stabilizer according to claim 1, wherein the starch dispersion is a dried product obtained by drying a liquid material irradiated with ultrasonic waves.

Invention of Claim 3 concerns on the emulsion stabilizer of Claim 1 or 2 in which the said raw material starch uses waxy corn starch as a main raw material.

Invention of Claim 4 concerns on the emulsion stabilizer of Claim 1 or 2 in which the said raw material starch uses corn starch as a main raw material.

According to the emulsion stabilizer according to the invention of claim 1, it is an emulsion stabilizer for an oil-and-fat-containing composition, wherein raw material starch is dissolved and gelatinized, and this is irradiated with ultrasonic waves to give a number average molecular weight (M _n ) of 40. since consisting × 10 ⁴ ~94 × 10 ⁴ and starch dispersion, procurement easier starch while as a raw material, it is possible to obtain a good emulsion stability than dextrin. In addition, no chemical treatment is required unlike chemical starch. Furthermore, the emulsion stabilizer which can also exhibit the oxidation inhibitory effect of fats and oils can be obtained.

  According to the emulsion stabilizer according to the invention of claim 2, in the invention of claim 1, since the starch dispersion is a dried product obtained by drying a liquid material irradiated with ultrasonic waves, preservative as an emulsion stabilizer And storage and handling are improved.

According to the emulsion stabilizer according to the invention of claim 3, in the invention of claim 1 or 2, since the raw material starch uses waxy corn starch as the main raw material, it has excellent stability at the time of gelatinization and easily and stably emulsifies. Can be obtained.

According to the emulsion stabilizer according to the invention of claim 4, in the invention of claim 1 or 2, since the raw material starch is corn starch as the main raw material, it has excellent stability at the time of gelatinization and has an easily stable emulsifying action. In addition to being obtainable, raw materials can be procured at low cost.

Preferred embodiments of the present invention will be described below with reference to the accompanying drawings.
FIG. 1 is a schematic process diagram of the emulsion stabilizer of the first embodiment, and FIG. 2 is a schematic process diagram of the emulsion stabilizer of the second embodiment.

  The emulsion stabilizer of the present invention is a stabilizer that is added to an oil-and-fat-containing composition and promotes emulsification between the oil-and-fat content and moisture in the composition as defined in claim 1. In addition, it is a stabilizer that also has an ability to inhibit oxidation of oils and fats and also suppresses oxidative degradation due to oxygen dissolved in water.

  The fats and oils are fatty acids such as butyric acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, etc. Fatty acids), and oils such as corn oil, soybean oil, rapeseed oil, olive oil, sesame oil, linseed oil, cottonseed oil, safflower oil, sunflower oil, perilla oil, peanut oil, palm oil, fish oil, Fats such as lard, het, and milk fat. In addition, in addition to various triacylglycerols, diacylglycerols, monoacylglycerols, waxes, phospholipids such as phosphatidylcholine, terpenes, and sterols can also be included.

  The oil-and-fat-containing composition corresponds to foods, beverages, cosmetics, pharmaceuticals, food additives and the like containing the listed fats and oils. The oil-and-fat-containing composition includes any composition form of “existence of oil and fat in moisture (for example, dressing and the like)” or “existence of moisture in oil and fat (for example, margarine and the like)”. In addition, various industrial oils such as machine cleaning oils, lubricating oils, cutting oils, engine oils, and the like are applicable.

The emulsification stabilizer of 1st Embodiment which is invention of Claim 1 is demonstrated using the schematic process drawing of FIG. Emulsification stabilizers are inexpensive and easily procured from starch. The raw material starch is once dispersed in water such as water, and is then gelatinized in a state where water molecules have entered the starch crystals appropriately by heating or the like (S11). Next, the gelatinized starch solution is irradiated with ultrasonic waves, and physical energy is applied to promote the reduction of the molecular weight of starch molecules (S12). Thus, the liquid substance (starch dispersion) in which starch molecules moderately reduced in molecular weight by ultrasonic irradiation are dispersed in water or the like is the emulsion stabilizer (P1) of the first embodiment.

  Further, details of each process will be described. In gelatinization (S11), the viscosity at the time of starch gelatinization is preferably taken into consideration from the viewpoint of equipment, including the type of starch, the amount of added water, and the emulsion stability. Mostly starches are prepared in the viscosity range of 0.2 to 40 Pa · s. In particular, since flowability between processes is taken into consideration, starch is preferably prepared within a viscosity range of 0.2 to 4 Pa · s.

When dissolving raw material starch, warm water and hot water are used from the viewpoint of work efficiency. In addition, according to the use of the emulsion stabilizer to be the product, in addition to water, dissolve starch in salt water, molasses water, a solution in which seasoning is dissolved, soup (bouillon), soup, sauce, sauce, etc. It is also possible to obtain a starch starch paste. In this case, moisture dilution of the food material to be added is avoided.

  In the ultrasonic irradiation (S12), the ultrasonic wave to be irradiated has a general frequency of 20 kHz to 1 MHz, and the output of the ultrasonic oscillator is also appropriately 100 to 2000 W. In the case of an extremely low frequency, energy such as vibration and impact associated with ultrasonic irradiation is low and does not contribute to the gelation of starch. When the frequency is extremely high, starch may be excessively liquefied and the molecular weight may be lowered too much, and the stability of emulsification may not be ensured. The irradiation time is comprehensively defined by the frequency, output, final viscosity, and the like.

  A treatment tank, an ultrasonic vibrator, an ultrasonic oscillator, and the like used for ultrasonic irradiation are appropriately selected in consideration of a production scale, a processing capability, and the like. The ultrasonic irradiation with respect to the starch gelatinized material may be either a sequential batch method or a continuous method.

Next, the emulsification stabilizer of the second embodiment which is the invention of claim 2 will be described using the schematic process diagram of FIG. As in the case of the first embodiment, the raw starch is once dispersed in moisture such as water, and is then gelatinized by a state in which water molecules have appropriately entered starch crystals by heating or the like (S21). Next, the gelatinized starch solution is irradiated with ultrasonic waves, and physical energy is added to promote the reduction of the molecular weight of starch molecules (S22). A liquid material (starch dispersion) in which starch molecules whose molecular weight has been reduced by ultrasonic irradiation is dispersed in water or the like is dried and processed into a dried product (S23). This dried product is the emulsion stabilizer (P2) of the second embodiment. Since dissolution / gelatinization (S21) and ultrasonic irradiation (S22) are the same as the apparatus and method described in detail in the emulsification stabilizer (P1) of the first embodiment, description thereof is omitted.

  In the drying (S23), freeze drying, drying with a vacuum drum dryer, spray drying (spray drying), or the like is used. By drying, convenience such as antiseptic, storage, and ease of handling is improved. Since starch-derived emulsion stabilizers are not desired to maintain taste and flavor, spray drying with excellent mass productivity is used. The shape of the dried product is not limited, such as powder or an indefinite shape such as flakes. In addition, it is preferable that it is a powder form from a viewpoint of the spreading | diffusion performance to an oil component / water component, and a particle size classification is performed as needed.

  In the gelatinization of the raw material starch of the second embodiment, if salt water other than water or a seasoning liquid is used, a dried product of a starch dispersion having a taste can be obtained. Such a dried product is preferable for maintaining the balance of the taste of the whole food product because it does not diminish the taste of the food material for use as a food additive. However, when starch molecules are dispersed in the seasoning liquid, it is preferable to use a vacuum drum dryer or the like in order to avoid a decrease in flavor.

The raw material starch used as the raw material of the emulsion stabilizer described so far is derived from corn, wheat, barley, rye, rice, sweet potato (sweet starch), potato (potato starch), pea, mung bean, tapioca and the like. Usually, the higher the amount of amylopectin, the more likely it is that precipitation and solidification tend not to occur after gelatinization. Therefore, as specified in the invention of claim 3, waxy corn starch is used as the main raw material for this raw material starch . Waxy corn starch is composed almost entirely of amylopectin. In addition to this, corn starch can be used as the main raw material for the raw starch , as shown in the examples described later and as defined in the invention of claim 4. When corn starch is used, very good emulsification stability can be obtained as compared to waxy corn starch (see Examples). Furthermore, since it can be procured at a low cost, manufacturing costs can be reduced.

  In the production of an emulsion stabilizer derived from starch, it is usually obtained by irradiating ultrasonically while appropriately controlling one kind of raw material starch (waxy corn starch or corn starch only) for ease of work. Furthermore, it is also possible to prepare the emulsion stabilizer by dispersing raw starches separately by ultrasonic irradiation and mixing different starch dispersions at a desired ratio afterwards. Of course, when irradiating raw material starch with ultrasound, a single type of starch is prepared for each different dose and post-mixed, or multiple types of starch are prepared for different doses and post-mixed, etc. Can be selected. The advantages of this method are as follows. For example, in the procurement of raw material starch, there may be fluctuations in quality due to environmental factors such as raw material harvesting place, harvest time, and harvest year. Therefore, the quality can be stabilized as much as possible by mixing the starch dispersions afterwards.

As disclosed in the examples below, the emulsifying action of fats and oils and moisture is recognized by the starch dispersion obtained by dissolving and gelatinizing the raw starch and irradiating with ultrasonic waves. However, the details of the mechanism of action relating to emulsification by the starch dispersion that has undergone ultrasonic irradiation are currently unknown. The inventors have estimated the following mechanism as the mechanism of action. In general, gelatinized starch swells to allow water molecules to enter between sugar chains constituting starch crystals, thereby forming a network-like polymer structure in which water molecules are held. Therefore, it exhibits the unique adhesion and elasticity found in starch paste. When the gelatinized starch is irradiated with ultrasonic waves, the network-like polymer structure is appropriately destroyed. As a result, it liquefies while maintaining affinity with water. At the same time, the hydrophobic part (lipophilic part) is also preserved because the polymer structure of starch is moderately maintained. That is, it can be considered that the affinity for both moisture and oil can coexist.

  Moreover, as disclosed in the background art, when water and fats and oils are stirred and emulsified, it is known that fats and oils are oxidized and deteriorated by oxygen and radical species dissolved in the water. . This is more pronounced for unsaturated fatty acids containing double bonds. In particular, the fat and oil content becomes finer with emulsification, and the contact surface area between the water and the fat and oil increases, so the influence of oxidation of the fat and oil cannot be ignored. As described above, the starch that has undergone ultrasonic irradiation disclosed as the present invention has a function as an emulsion stabilizer. After that, the inventors discovered that the starch that has undergone ultrasonic irradiation also has the effect of suppressing the oxidative deterioration of the mixed fat and oil while tracking changes over time in moisture, fat and oil, and starch-derived emulsion stabilizer (see below). See Examples).

  On the other hand, since the ultrasonic treatment itself is frequently used for emulsification of fats and oils, it is also possible to preliminarily mix starch and fats and carry out ultrasonic treatment to emulsify. However, it has been confirmed that the oxidation inhibition effect of starch in the present invention is expressed in starch after ultrasonic treatment. For this reason, it should be noted that in the case of ultrasonic treatment in which starch and fats and oils are mixed in advance, the effect is weak, and conversely, oxidative deterioration of fats and oils is likely to occur due to strong ultrasonic treatment. Therefore, it is desirable to mix with fats and oils after sonicating by mixing starch alone or a material that hardly causes deterioration.

  The suppression effect of oxidative degradation of fats and oils resulting from the starch-derived emulsion stabilizer of the present invention has not been clarified at present. The inventors consider this action as follows. Similar to the above-described mechanism of emulsification, the polymer structure of starch is moderately maintained and the hydrophobic part (lipophilic part) is preserved by ultrasonic irradiation of gelatinized starch. In connection with the affinity for both moisture and oil in this case, the hydrophobic portion of the fat and oil is protected by starch, and the contact between the hydrophobic portion of the fat and oil and the moisture is reduced. In this way, the oxidative deterioration which the hydrophobic part of fats and oils suffers is further suppressed.

  Therefore, in the emulsion-derived emulsion stabilizer of the present invention, in addition to stable emulsification performance, it also has an oxidation-inhibiting ability. It is used suitably for etc. In particular, even if it is not used in combination with other emulsifiers such as conventional starch (modified starch) or dextrin, sufficient emulsification stability can be exhibited when used alone. Therefore, it is effective even in the case of a simple composition consisting only of moisture and fats and oils. Specifically, in the field of foods and beverages, in addition to being added to mayonnaise, dressing, soup, roux, cream, margarine and the like, it is naturally included in food processed from these. In the field of pharmaceuticals and cosmetics, it is also effective when producing emulsions as external preparations or microcapsules carrying a drug. In addition, since it becomes an emulsifier also in the field of industrial oil waste oil treatment using microorganisms, it is beneficial. Obviously, since starch is a natural product, the environmental load is extremely small, and the emulsion stabilizer of starch itself has the advantage of becoming a nutrient.

  Also, according to the emulsion stabilizer derived from the starch dispersion that has been subjected to ultrasonic irradiation, after the oil-containing composition comprising water and fat and oil is once emulsified, the water is removed therefrom by drying and the starch dispersion and fat and oil are removed. Mixed solids with minutes can also be obtained. Perhaps as a result of the moderate maintenance of the high molecular structure of the starch, the hydrophobic part (lipophilic part) is also preserved, and the hydrophobic part of the fat is protected by starch. During drying, the evaporation of water not protected by starch proceeds, and it is considered that only the fat and oil are left behind in the starch.

  This is expected to have an effect as an excipient carrying oil and fat. In addition, since the oil that has been handled as a liquid is solidified, the performance of storage, weighing, and filling of the oil is improved, and the use for the above-mentioned foods, cosmetics, pharmaceuticals, and the like is also promising.

[Analytical equipment]
In the measurement of the number average molecular weight (M _n ), the gel filtration chromatograph method by HPLC was used. The differential refraction detector of the same device is manufactured by Shimadzu Corporation: RID-10A, the pump is manufactured by Shimadzu Corporation: LC-10ADvp, the column oven is manufactured by Shimadzu Corporation: CTO-10ASvp, and the column is TSKgel manufactured by Tosoh Corporation. α-M (7.8 × 300 mm) was used.

  Each of the prototypes and comparative examples were dissolved in pure water at a concentration of 1% by weight (w / v), filtered through a 0.45 μm membrane filter, loaded into the HPLC and measured. did. Pure water was used as the carrier, the flow rate was 1.0 mL / min, and the column temperature was 80 ° C. Showa Denko Co., Ltd .: SHODEX STANDARD P-82 (Pullane; weight average molecular weight 787000, 194000, 46700, 5900) was used as a molecular weight standard substance.

[Ultrasonic irradiation]
Using an ultrasonic disperser (manufactured by Ginsen Co., Ltd .: trade name “GSD1200CVP”), gelatinized starch was irradiated with ultrasonic waves while maintaining a liquid temperature of about 50 ° C. under conditions of a frequency of 20 kHz and an output of 1200 W. The amount of energy received by the starch was controlled by changing the ultrasonic irradiation time.

[Measurement of viscosity]
Evaluation of starch molecular weight reduction in starch gelatinized product by ultrasonic irradiation was based on the viscosity change of starch gelatinized material. The viscosity was measured in accordance with a viscosity measurement method in a general test method of the Japanese Pharmacopoeia, and the viscosity (Pa · s) was measured using a viscosity analyzer (trade name “TVB-10M” manufactured by Toki Sangyo Co., Ltd.).

[Dispersion of starch: Preparation of prototype examples 1, 2, 3, 4]
Waxy corn starch (manufactured by Nippon Shokuhin Kako Co., Ltd .: trade name “Waxy Starch”) was used as a raw material starch, water was added thereto, and gelatinized by a mini cooker (manufactured by Noritake Engineering Co., Ltd.). Next, using the above ultrasonic disperser, ultrasonic irradiation was performed under the same irradiation conditions and temperature for four types of irradiation times to prepare starch dispersion solutions of prototype examples 1 to 4. Each of the prototype examples 1 to 4 has a concentration of 20% by weight, and the measurement results of the viscosity and the number average molecular weight M _n are as shown in Table 1 below.

[Evaluation of emulsion stability]
In order to investigate the emulsion stability of the starch dispersions of Prototype Examples 1 to 4 obtained by the above preparation, after mixing the solution of each Prototype Example and edible oil, a cylindrical glass container (diameter 40 mm, height 120 mm) 100 mL each of the mixture of the solution of each trial example and edible oil was transferred and allowed to stand at room temperature for 3 days, and an overview of the presence or absence of separation of the oil layer, the mixed layer, and the aqueous layer was confirmed.

  Regarding the added amount of the starch dispersion of Prototype Examples 1 to 4, in any of the trial examples, 1 wt% (containing 4 g of solid content) and 5 wt% (containing 20 g of solid content) in terms of solid content in the final weight (400 g) , Mixed with 200 g of cooking oil while changing the amount of each of the prototype solutions so as to satisfy 8 wt% (containing 32 g of solid content) and 10 wt% (containing 40 g of solid content), and finally adding an appropriate amount of water. After mixing according to the weight of 400 g, the mixture was allowed to stand at room temperature for 3 days to confirm the appearance of layer separation.

  Prototype example 1-1: 1% by weight, prototype example 1-2: 5% by weight, prototype example 1-3: 8% by weight, prototype example 1-4: 10% by weight Prototype Example 2-1: 1% by weight, Prototype Example 2-2: 5% by weight, Prototype Example 2-3: 8% by weight, Prototype Example 2-4: 10% by weight Prototype Example 3-1: 1% by weight, Prototype Example 3-2: 5% by weight, Prototype Example 3-3: 8% by weight, Prototype Example 3-4: 10% by weight 4-1: 1% by weight, prototype example 4-2: 5% by weight, prototype example 4-3: 8% by weight, prototype example 4-4: 10% by weight, and so on. The weight% of each prototype is a numerical value in terms of solid content weight.

  The cooking oil used was salad oil (Nisshin Oillio Group Co., Ltd .: trade name “Nisshin Salad Oil”). In mixing, a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd .: trade name “TK HOMOMIXER”) and a rotor (TYPE M) were used, and the mixture was sufficiently suspended by stirring at 12,000 rpm for 15 minutes.

  For comparison with starch dispersions subjected to ultrasonic irradiation, dextrin and untreated starch were used in the comparative examples.

Comparative example 1
A waxy corn starch raw material dextrin (manufactured by Futamura Starch Co., Ltd .: trade name “FSD-301”) was used as a 20 wt% dextrin solution (Comparative Example 1). The number average molecular weight of Comparative Example 1 was 3100. Using the dextrin solution of Comparative Example 1, 1% by weight (containing 4 g of solid content; Comparative Example 1-1) in terms of solid content in the final weight (400 g), 5% by weight (containing 20 g of solid content; Comparative Example 1 2) 8% by weight (containing 32 g of solids; Comparative Example 1-3), 10% by weight (containing 40 g of solids; Comparative Example 1-4) After mixing with 200 g, adding an appropriate amount of water and mixing to a final weight of 400 g, the mixture was allowed to stand at room temperature for 3 days to confirm the appearance of layer separation.

Comparative example 2
Use the same waxy corn starch (manufactured by Nippon Shokuhin Kako Co., Ltd .: Waxy Starch) as in Prototype Examples 1 to 4, add water to this, and gelatinize with the above-mentioned mini cooker (manufactured by Noritake Engineering Co., Ltd.). % Gelatinized starch solution (Comparative Example 2). The number average molecular weight and viscosity of Comparative Example 2 were too high to be measured. Using the dextrin solution of Comparative Example 2, the final weight (400 g) in terms of solid content is 1 wt% (containing 4 g of solid content; Comparative Example 2-1), 5 wt% (containing 20 g of solid content; Comparative Example 2- 2) 8% by weight (containing 32 g of solids; Comparative Example 2-3), 10% by weight (containing 40 g of solids; Comparative Example 2-4) After mixing with 200 g, adding an appropriate amount of water and mixing to a final weight of 400 g, the mixture was allowed to stand at room temperature for 3 days to confirm the appearance of layer separation.

  The results of prototype examples 1-1 to 4-4 and comparative examples are shown in Table 2 below. The degree of separation of the emulsion stability was calculated by a volume percentage of “(volume of the separated oil layer after standing) ÷ (converted volume of edible oil present in the glass container at the start of standing) × 100”. The total amount separation is a state in which the total amount of the initially added oil is separated almost as it is. For example, when the oil content separated after standing is 50 mL and the initial amount of added oil is 50 mL, since the total amount is separated, the degree of separation is 100%. The evaluation items in the table are based on comprehensive judgment based on the degree of separation. “O” indicates no problem in emulsion stability. “△” is partially inferior in emulsion stability. “X” is not suitable for use because the emulsion stability cannot be confirmed.

[Results and discussion of emulsion stability]
In both prototypes and comparative examples, the solid content in the same concentration of oil and water is almost the same. From Table 2, the emulsion stability performance of starch dispersions subjected to ultrasonic irradiation is clear. In particular, even in a state where the fat and oil content is so large that half of the weight is occupied by the fat and oil, the emulsion stability can be obtained. This suggests that starch dispersions subjected to ultrasonic irradiation are adaptable to a wide range of fields.

The number average molecular weight of the starch dispersion subjected to ultrasonic irradiation is in the range of about 40 × 10 ^{4 to} 100 × 10 ⁴ (prototype examples 1 to 4). In particular, the number average molecular weight is in the range of 40 × 10 ^{4 to} 94 × 10 ⁴ (Prototype Examples 1 to 3). In contrast, the dextrin of the comparative example has a number average molecular weight of about 3000 of DE1 (dextrose equivalent) that is very lightly hydrolyzed by the enzyme. Further, the starch of the comparative example is expected to exceed the number average molecular weight of 100 × 10 ⁴ . The starch dispersion of the prototype is different from any of these molecular weight ranges.

  According to verification when waxy corn starch is used as a raw material starch, in order to obtain a stable emulsified state of oil and moisture, the number average molecular weight is preferably about several hundred thousand. Moreover, according to the said molecular weight, the effect is exhibited irrespective of the density | concentration of the starch dispersion in the whole. Therefore, the inventors consider the following factors that make the starch dispersion that has undergone ultrasonic irradiation a stable emulsified state.

  Oil absorption improves by making it porous, maintaining the particle | grain shape of starch like patent 3638645 etc. which were disclosed by background art. This action is due to the lipophilic nature of the starch particles. However, as in the gelatinized starch of Comparative Example 2, the lipophilicity is remarkably lost after the granular structure of starch is destroyed by heat gelatinization. In other words, it is considered that the fat and oil content hardly reaches the lipophilic part originally possessed by the starch molecule due to the increase in viscosity and the increase in adhesion accompanying the gelatinization of starch.

  Next, as in the dextrin of Comparative Example 1, when starch is enzymatically decomposed and liquefied, the number average molecular weight is decomposed to a chain length of about several thousand, so that the lipophilic part is not retained and the lipophilic property is maintained. It can be estimated that this disappears. In general, in a method in which gelatinized starch is liquefied by an enzyme, the number average molecular weight is reduced to about 3000 even if the degree of degradation is controlled to be extremely low as in DE1. Further attempts to reduce DE can be expected to have a low feasibility of the enzyme treatment method because of the considerable technical difficulty associated with sufficient mixing of starch and enzyme under high viscosity and control of the reaction.

  On the other hand, in the case of macromolecules that have undergone moderate degradation with a number average molecular weight of several hundreds of thousands as in Prototype Example 1 and Prototype Example 2 of starch dispersions subjected to ultrasonic irradiation, they are generally found in gelatinized starch. The effect of increased viscosity and increased adhesion is reduced. Therefore, the oil and fat can be reached relatively easily, and it can be assumed that a generally stable complex is formed.

[Evaluation of emulsion stability]
Inventors obtained the certainty about the emulsion stability of the starch dispersion which received ultrasonic irradiation as mentioned above, and mixed with various fats and oils, and verified the effect of emulsification. In addition, it was evaluated by the degree of separation out before the emulsion stability for other raw materials starch, including corn starch other than the waxy corn starch. The evaluation results are as shown in Table 3.

・ Prototype 5
The waxy corn starch of Prototype Example 1 was used as a raw material starch, water was added thereto, and gelatinized by the same mini-cooker. Using the ultrasonic disperser, ultrasonic irradiation was performed under the same irradiation conditions and temperature as in Prototype Example 1 to prepare a starch dispersion solution having a viscosity of 0.266 Pa · s and a concentration of 20% by weight at a temperature of 50 ° C. did. To 25 g of this starch dispersion solution, 100 g of soybean oil (manufactured by Kanto Chemical Co., Inc.) and 75 g of water were added, and the mixture was sufficiently suspended by stirring at 12,000 rpm for 15 minutes using the same homogenizer and rotor as described above. Then, the mixture was allowed to stand, and the appearance after 1 day and 7 days was observed as the degree of separation. In the following Prototype Example 16 and Prototype Example 17, the viscosity was adjusted to approximately the viscosity of Prototype Example 5 while appropriately adjusting the ultrasonic irradiation time.

-Prototype example 6
All the conditions were the same as in Prototype Example 5 except that the fat and oil was the salad oil used in Prototype Example 1 (Nisshin Oilio Group, Inc .: trade name “Nisshin Salad Oil”).

・ Prototype Example 7
All conditions were the same as those in Prototype Example 5 except that the oil and fat content was sesame oil (Nisshin Oilio Group Co., Ltd .: trade name “Scented Hikitatsugo Sesame Oil”).

・ Prototype Example 8
All conditions were the same as those in Prototype Example 5 except that the oil and fat content was margarine (manufactured by Snow Brand Milk Products Co., Ltd .: trade name “Snow Brand Neosoft”).

・ Prototype Example 9
All the conditions were the same as in Prototype Example 5 except that the fat and oil content was butter (manufactured by Snow Brand Milk Products Co., Ltd .: trade name “Kireru Snow Brand Hokkaido Butter”).

・ Prototype example 10
All conditions were the same as those in Prototype Example 5 except that the oil and fat was olive oil (manufactured by J-Oil Mills, Inc .: trade name “OLIVE OIL”).

・ Prototype 11
All the conditions were the same as in Prototype Example 5 except that the oil and fat was made from palm oil cosmetic oil (Living Wooden Co., Ltd .: trade name “handmade guild base oil COCONUT OIL coconut oil”).

・ Prototype Example 12
All the conditions were the same as in Prototype Example 5 except that the oil and fat content was made from macadamia nut oil cosmetic oil (Life Wood Co., Ltd .: trade name “handmade guild base oil MACADAMIA NUT macadamia nut oil (cosmetic oil)”).

・ Prototype Example 13
All the conditions were the same as in Prototype Example 5 except that the oil and fat content was changed to general industrial lubricating oil (manufactured by Cosmo Oil Lubricants Co., Ltd .: trade name “Cosmo Olpath 68”).

・ Prototype Example 14
All conditions were the same as those in Prototype Example 5 except that the oil and fat content was changed to an industrial compressor lubricating oil (manufactured by Idemitsu Kosan Co., Ltd .: trade name “Dafney New Rotary Compressor Oil”).

・ Prototype Example 15
All the conditions were the same as in Prototype Example 5 except that the oil and fat content was industrial turbine lubricating oil (manufactured by Idemitsu Kosan Co., Ltd .: trade name “Duffy Turbine Oil”).

・ Prototype Example 16
All the conditions were the same as in Example 5 except that the raw starch was changed from waxy corn starch to corn starch (Futamura Starch Co., Ltd.).

・ Prototype Example 17
All the conditions were the same as in Example 5 except that the raw starch was changed from waxy corn starch to potato starch (manufactured by Tokai Starch Co., Ltd.).

・ Prototype Example 18
Corn starch (manufactured by Futamura Starch Co., Ltd.) was used as the raw material starch, water was added thereto, and gelatinized with the same mini-cooker. Using the above ultrasonic disperser, applying the same irradiation conditions and temperature as in Prototype Example 1 and controlling the time of ultrasonic irradiation, a viscosity of 0.830 Pa · s and a concentration of 20% by weight at a temperature of 80 ° C. A starch dispersion solution was prepared. To 25 g of this starch dispersion solution, 100 g of soybean oil (same as in Prototype Example 5) and 75 g of water were added, and the suspension was sufficiently suspended by stirring at 12,000 rpm for 15 minutes using the same homogenizer and rotor as described above. Then, the mixture was allowed to stand, and the appearance after 1 day and 7 days was observed as the degree of separation. Prototype Example 18 corresponds to an example in which the ultrasonic irradiation conditions of Prototype Example 16 are changed.

・ Prototype Example 19
All the conditions were the same as in Prototype Example 18 except that the oil and fat content was the same salad oil as in Prototype Example 6.

・ Prototype Example 20
All the conditions were the same as in Prototype Example 18, except that the oil and fat content was the same sesame oil as in Prototype Example 7.

・ Prototype 21
All the conditions were the same as in Prototype Example 18 except that the oil and fat content was the same as margarine in Prototype Example 8.

・ Prototype Example 22
All the conditions were the same as in Prototype Example 18 except that the fat and oil was the same butter as in Prototype Example 9.

・ Prototype Example 23
All of the conditions were the same as in Prototype Example 18, except that the oil and fat was the same olive oil as in Prototype Example 10.

・ Prototype Example 24
All the conditions were the same as in Test Example 18 except that the oil and fat content was the same coconut oil as coconut oil as in Test Example 11.

・ Prototype Example 25
All the conditions were the same as in Prototype Example 18 except that the oil and fat content was the same macadamia nut oil cosmetic oil as in Prototype Example 12.

・ Prototype Example 26
All the conditions were the same as in Prototype Example 18, except that the oil and fat content was the same as general industrial lubricating oil as in Prototype Example 13.

・ Prototype 27
All the conditions were the same as in Prototype Example 18 except that the oil and fat content was the same industrial compressor lubricating oil as in Prototype Example 14.

・ Prototype Example 28
All the conditions were the same as in Prototype Example 18 except that the oil and fat content was the same industrial turbine lubricating oil as in Prototype Example 15.

Comparative example 3
Water was added to the corn starch used in the trial examples 16, 18 and the like, and gelatinized with the same mini cooker to obtain a gelatinized starch solution having a concentration of 20% by weight. Using this gelatinized starch solution, the subsequent treatment was suspended in the same manner as in Prototype Example 18 and then allowed to stand and observed. Comparative Example 3 is a control example of the presence or absence of ultrasonic irradiation in corn starch.

[Results and discussion of demonstration evaluation]
As shown in Table 3, the demonstration effect on emulsification of fats and oils mainly composed of fatty acids and the like of the starch dispersion subjected to ultrasonic irradiation was confirmed. This difference is clear from the comparison with Comparative Example 3. It is considered that the difference in emulsification stability for each fat or oil is affected by the difference in composition components or the influence of additives. From this result, performance can be secured as an emulsifier in the fields of food, medicine, cosmetics and the like. Moreover, it has confirmed that it was effective also about emulsification of industrial oil.

  Regarding the difference in emulsion stability observed for each type of starch, it was initially thought that the preservation of the molecular structure in which the sugar chains present in amylopectin were branched was affected. Therefore, we have been proceeding with verification mainly on waxy corn starch consisting almost of amylopectin. However, a comparison with common corn starch, which has a lower amylopectin content than waxy corn starch, revealed an improvement in the overall emulsion stability of fat and oil depending on the conditions of ultrasonic irradiation. In particular, the improvement in emulsification stability of industrial oils is remarkable. The inventors presume that in addition to the preservation of the branched molecular structure of amylopectin, there is also a helical linear structure of amylose, so that the capture of fat and oil by the amylose chain also contributes to emulsification. To do. The type of raw material starch can be appropriately selected according to factors such as the application of food, pharmaceuticals, etc., emulsification performance, and price in addition to the conditions of ultrasonic irradiation.

[Verification of oil adsorption performance]
In order to investigate the new function of starch dispersions subjected to ultrasonic irradiation, the oil adsorption performance was verified.

・ Experimental example 1
40 g of salad oil (same as in Prototype Example 6) and 160 g of water are added to 40 g of the starch dispersion solution using waxy corn starch prepared in Prototype Example 1, and the same homogenizer and rotor as above are used. Sufficiently suspended by stirring. Thereafter, the suspension was spread on a stainless steel vat, heated at 100 ° C. and dried.

・ Experimental example 2
The same amount of salad oil and water as in Experimental Example 1 were added to 40 g of the starch dispersion solution using corn starch prepared in Prototype Example 18, and suspended and dried under the same conditions.

Comparative example 4
In Comparative Example 4, the same conditions as in Experimental Example 1 were used except that the starch dispersion solution in Experimental Example 1 was changed to the dextrin solution (concentration 20% by weight) used in Comparative Example 1 above.

Comparative example 5
In Comparative Example 5, the same conditions as in Experimental Example 1 were used except that the starch dispersion solution in Experimental Example 1 was changed to the gelatinized starch solution (concentration 20% by weight) used in Comparative Example 2 above.

[Results and discussion of oil adsorption performance]
In Experimental Example 1, Experimental Example 2, Comparative Example 4, and Comparative Example 5, a dried product was obtained from Experimental Example 1 and Experimental Example 2. However, in all of the comparative examples, the oil content leached and a dried product could not be obtained. The experimental and comparative examples have substantially the same solid content and oil content. Only Experimental Examples 1 and 2 prevent oil from being separated by heating, and produce a dry product. That is, the starch dispersion (dried product) that has been subjected to ultrasonic irradiation stably retains oil and fat even at high temperatures. In the obtained results, there was no particular difference between starch species (difference between waxy corn starch and corn starch), and both could be dried. In addition, it is possible to use a suitable apparatus for the drying after mixing the said starch dispersion and fats and oils. For example, a homogeneous powder can be obtained by using spray drying or the like.

  From this result, the starch dispersion which received ultrasonic irradiation is fully effective as an excipient | filler which carries fats and oils. Therefore, it has high applicability in the fields of foods, pharmaceuticals, cosmetics, etc., and it is possible to study the production of powdered oils and fats, the use of fat-soluble drugs and vitamins carriers.

[Verification of oxidation inhibition effect]
The inventors who presumed that the starch dispersion subjected to ultrasonic irradiation formed a stable complex with the oil and fat also assumed the existence of an oxidation-inhibiting effect due to the stability. Therefore, the oxidation suppression effect was also verified. Based on the peroxide value (POV) measurement method described in “New Food Chemistry Experiment (issued in 2005, 3rd edition, p. 74)” issued by Kodansha Co., Ltd. / Kg of oil / fat ”was calculated and evaluated. The results are shown in Table 4.

Experimental example 3
To 40 g of starch dispersion solution using waxy corn starch prepared in Prototype Example 1, 200 g of soybean oil (same as Prototype Example 5) and 160 g of water are added, and using the same homogenizer and rotor as described above, 12000 rpm, 15 minutes Suspended sufficiently by rotary stirring (solid content 2%). Thereafter, 50 g of this suspension was poured into a screw spitz tube (internal volume: 50 mL), sealed and allowed to stand at room temperature. The peroxide value was measured immediately after suspension, after 5 days and after 28 days.

Experimental example 4
The same amount of soybean oil and water as in Experimental Example 3 was added to 40 g of the starch dispersion solution using corn starch prepared in Prototype Example 18, suspended under the same conditions, and allowed to stand for the same period.

Comparative Example 6
In Comparative Example 6, the starch dispersion solution of Experimental Example 3 was changed to the dextrin solution (concentration 20% by weight) used in Comparative Example 1 above, and 50 g of this dextrin solution was added with 200 g of soybean oil (same as in Prototype Example 5). 150 g of water was added (solid content 2.5%). All subsequent stirring and measurement were performed under the same conditions as in Experimental Example 3.

Comparative example 7
In Comparative Example 7, 200 g of soybean oil (same as in Prototype Example 5) was added to 200 g of water. All subsequent stirring and measurement were performed under the same conditions as in Experimental Example 3.

[Results and discussion of oxidation inhibition effect]
From Experimental Example 3 and Experimental Example 4, it can be seen that the progress of oxidation is suppressed from the comparison with Comparative Example 7. In particular, the longer the elapsed time, the more prominent, and the effect is also obtained at a low concentration. In the obtained results, there was almost no difference between starch species (difference between waxy corn starch and corn starch), and both showed the same effect. The dextrin of Comparative Example 6 also shows an oxidation inhibiting effect, but does not reach the effects of Experimental Examples 3 and 4.

  Based on this result, the inventors have formed a complex between the starch dispersion that has been subjected to ultrasonic irradiation and the fat and oil, thereby protecting the hydrophobic portion of the fat and oil from dissolved oxygen in water and other radical species. I expect that

  As mentioned above, the starch dispersion which received the ultrasonic irradiation disclosed in the Example acquired the knowledge which has both the emulsion stability and the oxidation inhibitory effect. Therefore, the starch dispersion which received ultrasonic irradiation has the very useful characteristic which has both the emulsification stability and oxidation suppression of oil-and-fat containing compositions, such as a foodstuff, and can be applied to a wide field | area.

It is a schematic process drawing of the emulsion stabilizer of 1st Embodiment. It is a schematic process drawing of the emulsion stabilizer of 2nd Embodiment.

Claims (4)

An emulsion stabilizer for an oil-containing composition comprising:
An emulsion stabilizer characterized by comprising a starch dispersion in which raw starch is dissolved and gelatinized, and the number average molecular weight (M _n ) is 40 × 10 ^{4 to} 94 × 10 ⁴ by irradiating with ultrasonic waves.   The emulsion stabilizer according to claim 1, wherein the starch dispersion is a dried product obtained by drying a liquid material irradiated with ultrasonic waves.   The emulsion stabilizer according to claim 1 or 2, wherein the raw starch is mainly waxy corn starch.   The emulsion stabilizer according to claim 1 or 2, wherein the raw starch is corn starch as a main raw material.

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