WO2014112276A1 - Esterified water-soluble soybean polysaccharide - Google Patents

Abstract

[Problem] The purpose of the present invention is to provide a polymer emulsifier having improved emulsifying power as compared with conventional polymer emulsifiers. [Solution] An esterified water-soluble soybean polysaccharide, having a structure in which one or more of the hydroxyl groups contained in arabinose residues and/or galactose residues constituting side chains are esterified with acetic acid.

Description

Esterified water-soluble soybean polysaccharide

The present invention relates to an esterified water-soluble soybean polysaccharide. Specifically, the present invention relates to an esterified water-soluble soybean polysaccharide in which at least a part of the hydroxyl group contained in the arabinose residue or galactose residue constituting the side chain is esterified, and an emulsifier and an emulsion containing the same.

As a conventionally known polymer emulsifier, amphiphilic property is imparted to a natural product such as gum arabic, water-soluble soybean polysaccharide or casein, or a synthetic product such as polyacrylate or polyvinyl alcohol, or starch. Semi-synthetic products such as octenyl succinic acid starch are mentioned. These polymer emulsifiers maintain the emulsified state without being destroyed even when the emulsion is highly diluted, and are excellent in stability to heating and stability under acidic conditions, so that they can be used for flavoring beverages. It is used as a base material for emulsified fragrances to be used.

Gum arabic stabilizes an oil-in-water (O / W type) emulsion by the function of a sugar chain in gum arabic as a hydrophilic group and a polypeptide bonded to the sugar chain as a hydrophobic group. Emulsions prepared using gum arabic are excellent for emulsifying fragrances because sugar chains form a thick hydrophilic layer at the oil droplet interface and gum arabic is less likely to separate at the oil droplet interface even when highly diluted. It is used as an emulsifier. However, in order to obtain an emulsified fragrance in a stable emulsified state, when the oil phase is 20% by weight, generally a high concentration of 12% by weight or more in the system (0.6 parts by weight or more per 1 part by weight of oil) is added. In addition, there is a problem that the supply amount fluctuates due to the climate and security situation of the producing country and the market price is not constant, and a polymer emulsifier that is excellent in emulsifying power and stability and that can be stably supplied is desired. (Non-Patent Document 1).

The water-soluble modified gum arabic having a weight average molecular weight of 900,000 or more obtained by heating gum arabic belonging to Acacia Senegal species is excellent in emulsifying power and emulsifying stability. However, in order to prepare an emulsion having an emulsified particle diameter of less than 1 μm in diameter, homogenization with a high-pressure homogenizer is required (Patent Document 1).

In addition, in order to obtain a stable emulsified fragrance using conventional water-soluble soybean polysaccharide, a large amount of addition is required as with gum arabic, and there is a problem that the viscosity of the emulsified fragrance is increased. Although a water-soluble soybean polysaccharide having a relatively low viscosity property has been reported (Patent Document 2), the emulsifying power is not sufficient, and further improvement of the emulsifying power is desired.

Furthermore, although synthetic polyacrylate or polyvinyl alcohol is excellent in emulsifying power, its use is limited because of its high viscosity.

On the other hand, there are various types of modified starches such as etherified starch, esterified starch, cross-linked starch, and grafted starch. Among them, octenyl succinic esterified starch, which is one of esterified starches, is excellent in emulsifying power, but in highly diluted systems such as emulsified fragrances, it has extremely low emulsification stability and can be stored for a long time. Not suitable for.

Furthermore, in addition to the above, Karaya gum is another natural polysaccharide containing a large amount of acetate. Karaya gum is partially soluble in water but mostly disperses and does not exhibit emulsifying power and emulsifying stability.

Special table 2006-522202 Japanese Patent Laid-Open No. 5-262802

Kuni ▲ Saki Naomichi, “Food polysaccharides: Knowledge of emulsification, thickening and gelation”, Koshobo (2001) pp. 77-84

As described above, conventional polymer emulsifiers such as gum arabic require a high amount of addition in order to exhibit sufficient emulsifying power. As a result, the viscosity of the emulsion is increased and the flavor is deteriorated. There was a problem of doing. In addition, there are problems in resistance to high dilution and stability of the emulsion. Accordingly, an object of the present invention is to provide a polymer emulsifier having improved emulsifying power as compared with conventional polymer emulsifiers.

As a result of various studies to achieve the above-mentioned object, the present inventors have determined that esterified water-soluble soybeans having a structure in which one or more hydroxyl groups of arabinose residues or galactose residues constituting the side chain are acetate-esterified. The present inventors have found that saccharides exhibit extremely high emulsifying power as compared with conventional natural water-soluble soybean polysaccharides that can have an acetate structure only in the main chain, and have completed the present invention.

That is, the present invention provides an esterified water-soluble soybean polysaccharide having a structure in which one or more hydroxyl groups contained in the arabinose residue and / or galactose residue constituting the side chain are esterified. In one embodiment, the acetate esterified structure is contained in an amount of 2% by weight or more in terms of free acetic acid with respect to 100% by weight of the total amount of the esterified water-soluble soybean polysaccharide.

The present invention also provides a production method for producing the esterified water-soluble soybean polysaccharide, comprising a step of subjecting the water-soluble soybean polysaccharide to an acetate esterification treatment. In one embodiment, the acetic esterification treatment is performed by mixing and reacting water-soluble soybean polysaccharide and acetic anhydride or vinyl acetate. In another embodiment, the mixed amount of acetic anhydride or vinyl acetate is 1 to 50 parts by weight with respect to 100 parts by weight of the dry weight of the water-soluble soybean polysaccharide.

The present invention also provides an emulsifier containing the esterified water-soluble soybean polysaccharide, and an oil-in-water emulsion formed using the emulsifier. In one embodiment, the oil-in-water emulsion contains 0.2 to 5 parts by weight of the esterified water-soluble soybean polysaccharide with respect to 1 part by weight of the oil content in the oil-in-water emulsion.

The present invention further provides use of the esterified water-soluble soybean polysaccharide for the preparation of an emulsifier.

According to the esterified water-soluble soybean polysaccharide of the present invention, the emulsifying ability and the emulsion stabilizing ability can be exhibited in a smaller amount than the conventional water-soluble soybean polysaccharide. In addition, according to the esterified water-soluble soybean polysaccharide of the present invention, the particle size of the emulsified particles can be reduced without causing an increase in the viscosity of the final product and a deterioration in flavor, and the particle size distribution of the emulsified particles is uniform. Therefore, it is possible to expand the range of blending into the final product.

In addition, in the production of an emulsion using a conventional polymer emulsifier such as gum arabic, the homogenization treatment with a high-pressure homogenizer is required several times, and the burden on equipment and work is large. According to the esterified water-soluble soybean polysaccharide, it is possible to reduce the particle size by only gentle stirring without performing homogenization with a high-pressure homogenizer. can do.

Furthermore, according to the esterified water-soluble soybean polysaccharide of the present invention, the obtained emulsion, particularly an oil-in-water emulsion, agglomerates or coalesces the emulsion particles by heating, long-term storage or change with time. Can be suppressed, and not only the emulsifying power but also the emulsification stability can be improved.

According to the production method of the present invention, the conventional natural water-soluble soybean polysaccharide can be easily subjected to acetate treatment, the yield is good, the production cost is suppressed, and the production process can be made more efficient.

FIG. 1 is a diagram of a MALDI-TOF-MS analysis spectrum of a side chain constituent sugar.

[Esterified water-soluble soybean polysaccharide]
In one embodiment, the esterified water-soluble soybean polysaccharide has a structure in which one or more hydroxyl groups contained in the arabinose residue and / or galactose residue constituting the side chain are acetated. The esterified water-soluble soybean polysaccharide can be produced from a water-soluble soybean polysaccharide obtained from soybean.

(Water-soluble soybean polysaccharide)
The water-soluble soybean polysaccharide used as a raw material is a water-soluble polysaccharide obtained from soybean by various known methods. For example, water-soluble soybean polysaccharide as described in Japanese Patent No. 2599477 can be mentioned. An example of production is a weakly acidic region near the isoelectric point of soy protein, such as pH 4-6, using okara or defatted soybean meal (meal) obtained as a by-product during production of tofu, soy milk or isolated soy protein. Thus, water-soluble soybean polysaccharide can be obtained by high-temperature extraction in an aqueous system and solid-liquid separation. In particular, okara at the time of producing separated soybean protein is preferable as a raw material because both oil and protein are low. The extraction temperature is preferably over 100 ° C. because the extraction efficiency is high. The upper limit of the extraction temperature is not particularly defined, but if it is carried out at an extremely high temperature, side reactions occur and coloration tends to occur, which is not preferable. Accordingly, the extraction temperature is usually 190 ° C. or lower, preferably 150 ° C. or lower, more preferably 130 ° C. or lower.

The water-soluble soybean polysaccharide as a raw material contains at least rhamnose, fucose, arabinose, xylose, galactose, glucose and uronic acid as main constituent sugars. For example, rhamnose 1-7% by weight, fucose 2-8% by weight And arabinose 15 to 50% by weight, xylose 2 to 10% by weight, galactose 25 to 60% by weight, glucose 4% by weight or less, and uronic acid 10 to 35% by weight. Uronic acid may include those in which the carboxyl group at the 6-position is methyl esterified, but the ratio is not particularly limited.

Water-soluble soybean polysaccharide has a highly branched sugar chain structure composed of a main chain and side chains. The main chain is composed of a homogalacturonan composed of galacturonic acid and a sugar chain containing rhamnogalacturonan composed of galacturonic acid and rhamnose, and optionally other sugars. The side chain is composed of a side chain composed of arabinan and galactan branched from the main chain rhamnose residue and a side chain composed of xylan branched from the main chain galacturonic acid residue. Among them, the galacturonic acid residue of the main chain may be naturally acetated like pectin, while the side chain does not contain an acetate structure.

Water-soluble soybean polysaccharides having an arbitrary molecular weight can be used as a raw material, but those having a weight average molecular weight of preferably 5,000 to 1,500,000, more preferably 50,000 to 1,000,000 are used. The weight average molecular weight is a value obtained by gel filtration HPLC using a TSK-GEL G-5000PWXL column (Tosoh Corporation) using standard pullulan (manufactured by Showa Denko KK) as a standard substance.

(Esterified water-soluble soybean polysaccharide)
The “esterified water-soluble soybean polysaccharide” in the present specification means a water-soluble structure having a structure in which one or more hydroxyl groups contained in the arabinose residue or galactose residue constituting the side chain are acetate esterified. It refers to soy polysaccharides. The acetated structure (also referred to as “acetate structure”) can be formed by reacting a water-soluble soybean polysaccharide with, for example, a compound that generates an acetate group.

The maximum number of acetate ester structures to be introduced is determined according to the number of hydroxyl groups contained in the arabinose residue or galactose residue in the side chain of the esterified water-soluble soybean polysaccharide. Even if is not introduced, the desired effect is achieved. In order to achieve the desired emulsifying power, the acetate structure is preferably 2% by weight or more, more preferably 3% by weight or more in terms of free acetic acid, based on 100% by weight of the total dry weight of the water-soluble soybean polysaccharide. . Although there is no particular limitation on the upper limit, even if it exceeds 10% by weight, there is no significant change in emulsifying power, and it may be 10% by weight or less. The method for quantifying the acetate structure contained in the esterified water-soluble soybean polysaccharide is as described below.

The weight average molecular weight of the esterified water-soluble soybean polysaccharide may vary depending on the molecular weight of the water-soluble soybean polysaccharide used as a raw material, but is preferably 5,000 to 1,500,000, more preferably 50,000 to 1,000,000. The weight average molecular weight is a value obtained by gel filtration HPLC using a TSK-GEL G-5000PWXL column (Tosoh Corporation) using standard pullulan (manufactured by Showa Denko KK) as a standard substance.

Esterified water-soluble soybean polysaccharide has higher emulsifying power than gum arabic or non-esterified water-soluble soybean polysaccharide, and the obtained emulsion has high emulsion stability. Here, "emulsifying power" refers to the ability to adsorb to the interface between non-mixed substances such as water and oil, and to uniformly disperse one to the other and maintain that state. Can be evaluated by On the other hand, “emulsification stability” or “emulsion stability” means that the emulsion particle diameter of the emulsion becomes significantly large during storage or the emulsified interface is destroyed and the emulsified substance is released. It refers to maintaining the state of the emulsion, and can be evaluated by, for example, changes in the emulsion particle diameter over time or the release of the emulsified substance over time.

[Method for producing esterified water-soluble soybean polysaccharide]
Although the manufacturing method of esterified water-soluble soybean polysaccharide is not specifically limited, In one Embodiment, the process of performing an acetic acid esterification process with respect to the water-soluble soybean polysaccharide obtained from soybean is included.

(Acetic acid esterification treatment)
The water-soluble soybean polysaccharide which is the raw material for the esterification treatment is as described above. It may be a natural product or a processed water-soluble soybean polysaccharide subjected to other treatments. Further, for example, it may be an extract filtrate of a water-soluble soybean polysaccharide or a purified product of the extract filtrate, or may be a product obtained by further drying the extract filtrate or a purified product thereof.

Examples of the acetic acid esterification treatment method include an aqueous solution of a raw material water-soluble soybean polysaccharide, or a mixed solution of the aqueous solution and a polar organic solvent such as alcohol and acetone, for example, acetic anhydride, vinyl acetate, glacial acetic acid, chloride. It is carried out by mixing and reacting substances that form a hydroxyl group and acetate such as acetyl and ketene. Among the substances forming the hydroxyl group and acetate, acetic anhydride and vinyl acetate are preferable from the viewpoint of production safety. In the case of glacial acetic acid, safety is high but reactivity may be weak. In the case of acetyl chloride, there is a danger of reacting violently with water. In the case of ketene, there is a problem that it is difficult to handle because of toxic gas. The acetic esterification treatment is preferably performed by mixing and reacting water-soluble soybean polysaccharide with acetic anhydride or vinyl acetate.

The reaction is carried out with stirring while maintaining the pH at preferably 5 to 10, more preferably 7 to 9 (neutral to weakly alkaline). If the pH is lower than 5, water-soluble soybean polysaccharides may not be sufficiently esterified. Further, even if the pH is higher than 10, water-soluble soybean polysaccharides may be detached and sufficient esterification may not be performed. Since the pH of the reaction solution is lowered during the reaction, the alkali agent is preferably added in the form of a solid or a solution in order to maintain the pH from neutral to weakly alkaline. Examples of the alkali agent added at this time include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, and alkali metal hydroxides such as potassium carbonate, sodium carbonate, lithium carbonate, and sodium hydrogen carbonate. Organic salts of alkali metals such as carbonate, sodium citrate and sodium oxalate, inorganic salts of alkali metals such as trisodium phosphate, and hydroxides of divalent metals such as calcium hydroxide and magnesium hydroxide As well as ammonia.

The reaction temperature may be appropriately adjusted to a temperature at which the reactant is completely dissolved in the reaction solution, and is preferably 0 ° C. or higher and 60 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower. When the temperature is higher than 60 ° C., for example, in the case of acetic anhydride, hydrolysis may be accelerated, and there may be an increase in those that decompose into acetic acid without reacting with the water-soluble soybean polysaccharide.

The mixing amount of the substance that forms a hydroxyl group and an acetate used in the acetate esterification treatment is preferably 1 to 50 parts by weight, more preferably 2 to 2 parts by weight based on 100 parts by weight of the dry weight of the water-soluble soybean polysaccharide. 40 parts by weight, more preferably 3 to 30 parts by weight is suitable. If the mixing amount is too small (for example, less than 1 part by weight), the esterification may not be sufficiently performed. Moreover, even if there is too much addition amount (for example, the amount exceeding 50 weight part), there may be no difference in the efficiency of acetic esterification.

(Purification and other processes)
After the acetic esterification treatment, in some cases, a step of purifying the water-soluble soybean polysaccharide after the acetic esterification treatment by a purification treatment may be performed. You may perform a refinement | purification process with respect to the water-soluble soybean polysaccharide of a raw material.

As the purification treatment, water-soluble soybean polysaccharides after the acetic esterification treatment, preferably water-soluble soybean polysaccharides neutralized after the acetic esterification treatment, are desalted and / or deproteinized as necessary. Is given.

The desalting purification method may be any method that can separate and remove salts. Reprecipitation using a polar organic solvent such as methanol, ethanol, isopropanol, and acetone, activated carbon treatment, resin adsorption treatment, ultrafiltration method, reverse osmosis method, gel filtration method, dialysis method, ion exchange resin method, electricity A dialysis method and an ion exchange membrane method can be exemplified, and only one of these may be performed, or two or more may be combined. The method of deproteinization is a method of aggregating proteins by adjusting pH near the isoelectric point of soybean protein with acid or alkali, and removing the aggregates by pressure filtration separation, centrifugation, filtration, membrane separation, etc. Examples thereof include a method for decomposing using a known protease, a method for removing by adsorption using activated carbon or a resin, and the like. It is desirable to remove contaminating proteins by combining one or more of these.

In addition to the purification treatment, the solution of the unpurified or purified esterified water-soluble soybean polysaccharide may be subjected to concentration treatment and sterilization treatment such as plate sterilization or steam sterilization as necessary, and further subjected to drying treatment. Also good. Examples of the drying method include freeze drying, spray drying, drum dryer drying, and the like, and if necessary, pulverization can be performed after drying. These drying methods can be appropriately selected depending on the state of the water-soluble soybean polysaccharide before the drying treatment.

(Quantification method of acetate structure)
The content of the acetate ester structure in the water-soluble soybean polysaccharide is determined by the relative content of the acetate ester structure with respect to the entire water-soluble soybean polysaccharide, here, the amount of acetic acid (% by weight). For example, acetic acid ester-bonded to water-soluble soybean polysaccharide is hydrolyzed, and liberated acetic acid is quantified by ion chromatography. For example, according to the following formula I, acetic acid ester contained in esterified water-soluble soybean polysaccharide is converted into acetate. The corresponding amount of acetic acid is determined. That is, the amount of acetic acid obtained by the formula I is defined as “the amount of the structure esterified” obtained in terms of free acetic acid.
Amount of acetic acid = 1.4 × V2-V1 (Formula I)

In the above formula, V1 is the amount of acetic acid measured by ion chromatography with respect to the water-soluble soybean polysaccharide before ester decomposition. For example, 5 ml of a 0.3% by weight solution of the water-soluble soybean polysaccharide as a sample has a molecular weight of 10,000. The liquid passed through the cut filter is used as a sample, and the amount of acetic acid contained in the sample solution is measured by ion chromatography. V2 is, for example, 1 ml of 0.5N sodium hydroxide is added to 5 ml of a 0.3% by weight solution of the same sample and subjected to ester decomposition treatment at 40 ° C. for 20 minutes. The solution that has been added and passed through a filter having a molecular weight of 10,000 after neutralization is used as a sample, and the amount of acetic acid contained in this sample solution is similarly measured by ion chromatography. “1.4 ×” is a correction coefficient ((5 + 1 + 1) ml / 5 ml) for the amount of diluted sample. The amount of acetic acid derived from the acetic acid ester contained in the water-soluble soybean polysaccharide is determined by the above calculation formula.

For example, Compact IC 861 (manufactured by Metrohm Japan) is used for ion chromatography, the column is Shodex RS Pak KC-811 (φ8 mm × 300 mm), 50 ° C., the eluent is 1 mM perchloric acid (flow rate 1 ml / min), detector. In addition, an electrical conductivity detector is used, and sodium acetate is used as the standard substance.

(Qualitative analysis method for acetic esterification of sugars constituting side chains)
The degree of acetic esterification in the obtained esterified water-soluble soybean polysaccharide is, that is, acetic acid of the sugar constituting the side chain of the water-soluble soybean polysaccharide (sometimes referred to as “side-chain constituent sugar” in this specification). The degree of esterification can be analyzed by mass spectrometry. For example, esterified water-soluble soybean polysaccharide is adjusted to a final concentration of 0.1% in a 50 mM sodium acetate buffer (pH 5.5), and a cellulase enzyme agent derived from basidiomycetes, such as Driselase (manufactured by Kyowa Hakko), 40 ° C. Decomposes at least 18 hours. After the enzymatic reaction was stopped by boiling for 10 minutes, the liquid passed through a 10,000 molecular weight cut filter (Amicon Ultra Ultra-10 membrane; manufactured by Merck) was collected, and the reducing sugar concentration measured by the Somogyi-Nelson method was 300 μg / Make sure that it has been broken down to more than ml. 1 ml of the filtered solution is dried under reduced pressure, and the dried product is dissolved in 10 μl of a 0.1% trifluoroacetic acid / acetonitrile 1: 1 mixed solution. The lysate and an appropriate matrix are mixed to prepare an analysis sample, which is subjected to, for example, MALDI-TOF-MS analysis.

[Use of esterified water-soluble soybean polysaccharide]
(emulsifier)
Esterified water-soluble soybean polysaccharides can exhibit emulsifying power and dispersion stability of the emulsion with a small amount, which is difficult to solve with the prior art. In addition, the emulsifying power can be exerted only by gentle stirring without using a device with high market share such as a high-pressure homogenizer. Furthermore, since it has less influence on the flavor, a wider variety of oil-in-water types (O / (W-type) emulsion or W / O / W-type emulsion can be used as an emulsifier.

In particular, in order to prepare an oil-in-water emulsion or a W / O / W emulsion not only in foods but also in the fields of pharmaceuticals, quasi drugs, cosmetics, etc. in order to have excellent dispersion stability of the emulsion. It can also be used as an emulsifier.

Specific uses of the esterified water-soluble soybean polysaccharide as an emulsifier include foods such as soft drinks, milk drinks, soybean drinks, fruit juice drinks, teas, sports drinks, powder drinks, and alcoholic drinks, candy , Gummy, jelly, chewing gum and other confectionery, ice cream and other frozen confectionery, dressing, mayonnaise, bakery products, marine products, livestock products, retort foods and other foods, emulsification of oily flavors In addition, it can be used as an emulsifier for emulsification of oily pigments and the like. Moreover, it is also effective to add to these food-drinks as an emulsified fragrance | flavor mentioned later.

Non-food applications include shampoos and rinses, hair treatments such as hair treatments, hair lotions, and waxes, lipsticks, lotions, cleansing creams, shaving foams, facial cleansers, emulsions, hand soaps, foundations. , Moisturizing essence, body shampoo, makeup remover and other skin cosmetics, paints, anti-cancer drugs and other quasi-drugs and coatings, bathing agents, clothing detergents, residential detergents, etc. These emulsifiers can be used as emulsifiers for daily commodities, pesticides such as insecticides and herbicides, processing agents such as paints, inks and waxes, other chemical products, feeds, and printed materials.

The esterified water-soluble soybean polysaccharide can be used as an emulsifier in the form of a solution or dried and powdered, but it can also be used as an emulsifier by blending other carriers and additives. In this case, the carrier and additive to be used can be appropriately selected depending on the type and use of the product using the emulsifier. For example, a water-soluble soybean polysaccharide can be used by mixing with a polyhydric alcohol such as glycerin or a saccharide such as dextrin and lactose.

(Emulsifying flavor)
As another advantageous use of the esterified water-soluble soybean polysaccharide, use for emulsified flavors and the like is exemplified. The emulsified fragrance is an oil-in-water (O / W type) emulsion obtained by emulsifying a phase composed of a hydrophobic substance obtained by dissolving a refined essential oil or a blended fragrance in a vegetable oil using an emulsifier.

When the esterified water-soluble soybean polysaccharide is used in the emulsified flavor, the esterified water-soluble soybean polysaccharide is added in an amount of 0.2 to 5 parts by weight, preferably 0. Add 5 to 3 parts by weight. For example, in the case of an emulsified flavor containing 10% by weight of the oil layer, the esterified water-soluble soybean polysaccharide is contained in the emulsified flavor by 2 to 50% by weight. On the other hand, in the conventional gum arabic, if the amount exceeding 12% by weight (0.6 parts by weight or more with respect to 1 part by weight of oil) is not added to the oil phase, the emulsification force is insufficient, and the emulsified particle size is increased over time. And the long-term emulsion stability tends to be impaired. Therefore, the esterified water-soluble soybean polysaccharide of the present invention is a small amount compared to gum arabic in that sufficient emulsifying power can be exerted even if the addition amount is less than 0.6 parts by weight relative to 1 part by weight of oil. It has excellent emulsifying power and emulsifying stability, and has a remarkable effect that an increase in the viscosity of the emulsion can be suppressed. In addition, in the case of the emulsified fragrance | flavor used for the alcoholic beverage mentioned later, even when it is a case where an emulsifier is used in high concentration, it has a remarkable effect compared with gum arabic.

The hydrophobic substance emulsified in the emulsified perfume is not particularly limited as long as it is normally used in the dispersed phase of the emulsified perfume. Specifically, examples of oily flavors include citrus essential oils such as orange, grapefruit, summer tangerine, bergamot, lime, lemon and yuzu, plant essential oils such as flower essential oil, spearmint oil and peppermint oil, onion, garlic and cardamom. , Cumin, clove, ginger, celery, nutmeg, basil, parsley, paprika, black pepper, rosemary, laurel and other spices essential oil or oleoresin, cola nut extract, coffee extract, cocoa extract, tea Oily extracts such as extract, spice extract, and vanilla extract and their oleoresins, eugenol, geraniol, acetic acid, diacetyl, citral, vanillin, ethyl propionate, men Lumpur, butyric, and flavoring substances such as limonene, synthetic perfume compounds, oily blended fragrance composition, and the like of any of these mixtures thereof.

Examples of animal and plant oils and fats added to the above oily flavors include olive oil, cacao butter, corn oil, sesame oil, wheat germ oil, rice oil, rice bran oil, safflower oil, soybean oil, camellia oil, rapeseed oil, and palm oil. , Sunflower oil, cottonseed oil, palm oil, peanut oil, beef tallow, lard, chicken oil, fish oil, and butter. Examples of the medium chain saturated fatty acid triglycerides include those having 6 to 12 carbon atoms such as caproic acid triglyceride, caprylic acid triglyceride, capric acid triglyceride, and lauric acid triglyceride, which are used as processed edible oils. Examples of the oil-soluble pigments include oil-soluble natural pigments such as Anato pigment, chlorophyll, β-carotene, and paprika pigment. Examples of oil-soluble vitamins include liver oil, vitamin A, vitamin A oil, vitamin B2 butyrate ester, vitamin D3, and natural vitamin E mixture. Examples of natural resins include vegetable resins such as Elemi, ester gum, corbal, dammar, and rosin.

These edible oily materials can be used alone or in the form of a mixture of two or more.

The emulsified fragrance containing the esterified water-soluble soybean polysaccharide is particularly preferably used as an emulsified fragrance for alcoholic beverages. The alcoholic beverage refers to any beverage containing 3 to 50% by volume of ethyl alcohol, preferably 3 to 10% by volume, and examples thereof include conch syrup, chuhai, sour, cocktail, liqueur, and sweet fruit wine. . The conventional polymer emulsified fragrance lacks the function of suppressing oil floating while maintaining the turbidity due to the emulsified particles during storage, and is particularly conch syrup for alcoholic beverages containing 20% by volume or more of ethyl alcohol. It was remarkable. Emulsified fragrances using esterified water-soluble soybean polysaccharides are remarkably high in emulsification stability when used in these alcoholic beverages and conch syrups, and are most suitable for alcoholic beverages, compared to commonly used gum arabic. .

(Emulsion)
An oil-in-water emulsion formed using an emulsifier containing an esterified water-soluble soybean polysaccharide is generally liquid or solid. Specific examples include beverages such as soft drinks, milk drinks, soy drinks, fruit juice drinks, tea, sports drinks, powder drinks, alcoholic drinks, seasoning sauces such as sauces, sauces, dressings, ketchup and mayonnaise, corn soup and Soups such as potage, roux such as curry roux and stew, pastes such as vegetable paste, fruit paste, seafood paste, flower paste and flavor paste, spreads such as jam, fruit spread, milk spread and peanut butter, Milk / fat products such as butter, cheese, margarine, and cream, ice cream, soft cream, sorbet, frozen confectionery such as ice candy, pudding, bavaroa, jelly, yogurt and other desserts, rice cake, caramel, gum, Gummy, Marshmallow , And sweets such as chocolate and the like.

As a method for preparing the emulsion, a known general method can be used. For example, after dissolving the water-soluble soybean polysaccharide in water or a hydrophilic solvent capable of dissolving the water-soluble soybean polysaccharide and adding the hydrophobic substance, the mixture may be mixed and stirred using an appropriate apparatus in some cases. Or processing, such as homogenization, is performed and an emulsified solution is prepared. As needed, before or after emulsification, sugars such as fructose glucose liquid sugar and sorbitol, polyhydric alcohols such as glycerin and propylene glycol, preservatives, antioxidants, pH adjusters and other additives, salts, organic Acids, fruit juices, pigments, fragrances, and the like may be added, or pH adjustment may be performed. In the case of emulsification by mixing, stirring, homogenization or the like, the solution may be heated or cooled.

Various devices as an emulsifying apparatus for producing and stabilizing the emulsion can be used, and can be appropriately selected according to the particle size, viscosity, etc. of the target oil-in-water emulsion. In some cases, the object can be achieved not only by an emulsifier such as a high-pressure homogenizer and an ultrasonic homogenizer, but also by a mixer such as a colloid mill, a disper mill, a homomixer, and a propeller stirrer. For example, gum arabic, which is a representative of conventional polymer emulsifiers, needs to be pre-emulsified with a homomixer in advance to prepare an emulsion having a certain particle size, and then homogenized with a high-pressure homogenizer, which is an expensive device. Met. When the esterified water-soluble soybean polysaccharide is used, a fine and uniform oil-in-water emulsion can be obtained only by gentle stirring without using a high-pressure homogenizer, which may lead to labor saving. Therefore, the manufacturing cost of the emulsion can be suppressed, and the manufacturing process can be made more efficient. In addition, fluorescent paints and toners can be prepared to a particle size of 1 to 3 μm only by pre-emulsification without using a high-pressure homogenizer, or for dressings used for salads, etc., even after shaking. There is an advantage that a stable particle diameter can be maintained for a while.

Hereinafter, the present invention will be described more specifically by way of examples. In the examples, “%” means “% by weight” unless otherwise specified.

Comparative Example 1 Preparation of Untreated Water-Soluble Soy Polysaccharide Okara produced during the production of isolated soy protein was used as a raw material, and water was added thereto, and the pH was adjusted to 5 with hydrochloric acid. Subsequently, it heated at 125 degreeC and 2 hours using the pressurization pot, and extracted water-soluble soybean polysaccharide. The extract was centrifuged (5,000 × g, 10 minutes) to separate into a supernatant and a precipitate mainly containing water-soluble soybean polysaccharide. A part of the supernatant was freeze-dried to obtain an untreated water-soluble soybean polysaccharide Z.

(Example 1) Preparation of esterified water-soluble soybean polysaccharide (1)
A 10 wt% solution of water-soluble soybean polysaccharide Z was prepared, and adjusted to pH 8 by adding sodium hydroxide. While stirring at a pH of 8 with an automatic titrator, 6% by weight of acetic anhydride was added in small portions over 30 minutes with respect to the solid content of the water-soluble soybean polysaccharide, followed by esterification for 1 hour. . Hydrochloric acid was added to the solution to adjust to pH 5, and twice the amount of ethanol was added to precipitate the polysaccharide. The precipitate was washed twice with ethanol and then air-dried to obtain esterified water-soluble soybean polysaccharide A.

(Example 2) Preparation of esterified water-soluble soybean polysaccharide (2)
In the production of the esterified water-soluble soybean polysaccharide A in Example 2, esterified water-soluble soybean polysaccharide B was obtained in the same procedure as in Example 1 except that the amount of acetic anhydride added was 8% by weight.

(Quantification of the degree of acetate esterification)
For the various water-soluble soybean polysaccharides obtained in Comparative Example 1 and Examples 1 and 2, the degree of acetate formation was measured by ion chromatography according to the above-mentioned “Method for quantifying acetate structure”, and the formula (I) Was calculated and quantified. The quantified value (acetic acid amount) is shown in Table 1. Compared with water-soluble soybean polysaccharide Z having a natural acetate structure in the main chain, esterified water-soluble soybean polysaccharides A and B in which side chain constituent sugars are esterified have higher acetic acid contents.

(MALDI-TOF-MS analysis spectrum of side chain constituent sugars)
The esterified water-soluble soybean polysaccharide B obtained in Example 2 was subjected to MALDI-TOF-MS analysis of the enzymatic degradation product according to the above-described “qualitative analysis method for acetate esterification of sugars constituting the side chain”. It was. Specifically, the basidiomycete-derived cellulase enzyme Driselase (Kyowa Hakko) was added to 2.1 ml of an esterified water-soluble soybean polysaccharide having a final concentration of 0.1% in 50 mM sodium acetate buffer (pH 5.5). 0.9 ml) was added and allowed to undergo a decomposition reaction at 40 ° C. for 18 hours or longer. After stopping the enzymatic reaction by boiling for 10 minutes, the liquid passed through a 10,000 molecular weight cut filter (Amicon Ultra Ultra-10 membrane; manufactured by Merck) was collected, and the reducing sugar concentration measured by the Somogyi-Nelson method was 300 μg / It was confirmed that the product was decomposed until the volume became more than ml. 1 ml of the liquid passing through the filter was dried under reduced pressure, and the dried product was dissolved in 10 μl of a 0.1% trifluoroacetic acid / acetonitrile 1: 1 mixed solution. The lysate and an appropriate matrix were mixed to prepare an analysis sample, which was subjected to MALDI-TOF-MS analysis. The analytical spectrum is shown in FIG. A plurality of mass peaks corresponding to a structure in which the arabinose residue and galactose residue, which are side-chain constituent sugars, contain a 1-residue or 2-residue acetate structure were confirmed. These peaks were not confirmed in the analysis spectrum of the decomposition product of the water-soluble soybean polysaccharide Z of Comparative Example 1 in which acetic esterification reaction was not performed.

(Examples 3 to 4 and Comparative Example 2) Preparation of Emulsion Composition Using the water-soluble soybean polysaccharide Z of Comparative Example 1 and the esterified water-soluble soybean polysaccharides A and B of Examples 1 and 2, Therefore, the emulsion compositions of Examples 3 to 4 and Comparative Example 2 were prepared.

16.0 g of glycerin is added to 100 g of distilled water, and 21.4 g of water-soluble soybean polysaccharide Z and esterified water-soluble soybean polysaccharides A to B are dissolved with stirring, and pH is 4.0 with 50% citric acid solution. Adjusted. Next, lemon oil, MCT (medium chain fatty acid triglyceride) and sucrose diacetate hexisobutyrate (sucrose diacetic acid hexaisobutyrate ester) were mixed in advance so that the weight ratio was 2: 3: 5 (specific gravity d 1.010). Was added to an aqueous solution of various water-soluble soybean polysaccharides, water was further added until the total amount became 200 g, and the mixture was kept at 45 ° C. The heated solution was pre-stirred with a homogenizer “Polytron” (manufactured by KINEMATICA) for 10 minutes under the condition of 10,000 rpm, and further using a high-pressure homogenizer “Minilab 8.30H type” (manufactured by RANNIE), pressure 150 kgf / cm 2 Homogenization was performed twice at (14.71 MPa) to obtain the emulsified compositions of Examples 3 to 4 and Comparative Example 2. Each emulsified composition was stored refrigerated, and the median particle size immediately after preparation and on the 7th day was measured with a laser diffraction particle size distribution analyzer “SALD2000A” (Shimadzu Corporation). The results are shown in Table 2.

When esterified water-soluble soybean polysaccharides A and B were used, a fine emulsion having a median diameter of 0.4 μm could be prepared. The particle size distribution was uniform, and the emulsion was stable without significant changes even after 7 days of refrigerated storage. When water-soluble soybean polysaccharide Z is used, the median diameter is larger than the median diameter when esterified water-soluble soybean polysaccharide A or B is used, and it tends to be slightly larger with refrigerated storage. It was.

(Examples 5 to 6 and Comparative Example 3) Preparation of Conyrup Syrup The stability evaluation of the emulsified compositions of Examples 3 to 4 and Comparative Example 2 under conditions with high acidity and high alcohol concentration (conclusion syrup stage of alcoholic beverages) Went. In 60 g of water, 1.14 g of citric acid, 0.33 g of sodium citrate and 11.8 g of isomerized sugar were dissolved, 21 ml of ethanol was added, and the volume was made up to 100 ml with water to obtain a consyrup. 0.3 g of the emulsion composition of Examples 3 to 4 and Comparative Example 2 was added to this consyrup and stored at room temperature. Oil floatation, turbidity (OD 680), median particles immediately after preparation and on the third day The diameter (laser diffraction particle size distribution measuring device) was measured, and the results are shown in Table 3.

When the esterified water-soluble soybean polysaccharide A or B was used, the median diameter of the emulsion was as fine as 0.4 μm, and a stable state was maintained without oil floating until after 3 days. The emulsion when water-soluble soybean polysaccharide Z is used is smaller than the median diameter of 0.8 μm of a general gum arabic gum emulsion, but compared with the case where esterified water-soluble soybean polysaccharide A or B is used. Was also big. Moreover, many oil floats were produced during storage, and the emulsion stability was lacking.

(Examples 7 to 9 and Comparative Examples 4 to 6) Low share preparation of emulsion composition (1)
Using the water-soluble soybean polysaccharide Z and the esterified water-soluble soybean polysaccharide B, each emulsion composition was prepared by the following procedure without using a high-pressure homogenizer.

Esterified water-soluble soybean polysaccharide B or water-soluble soybean polysaccharide Z 16 g was dissolved in 48 g of distilled water with stirring, and adjusted to pH 4.0 with a 50 wt% citric acid solution. Next, lemon oil, MCT (medium chain fatty acid triglyceride) and sucrose diacetate hexisobutyrate (sucrose diacetic acid hexaisobutyrate ester) were mixed in advance so that the weight ratio was 2: 3: 5 (specific gravity d 1.010). Was added to various water-soluble soybean polysaccharide solutions, and water was further added until the total amount reached 100 g, followed by ice cooling. The ice-cooled solution was stirred with a stirrer “Polytron” (manufactured by KINEMATICA) for 60 minutes under the condition of 7,500 rpm to obtain each emulsion composition of Example 7 and Comparative Example 4. At that time, in order to confirm the emulsified state in 20 minutes of stirring, a minimum sample necessary for measuring the particle diameter was collected.

Further, the emulsion compositions of Examples 8 to 9 and Comparative Examples 5 to 6 were obtained by the same prescription and procedure as described above except that the rotation speed of stirring was changed to 5,000 rpm or 2500 rpm.

For the emulsified compositions of Examples 7 to 9 and Comparative Examples 4 to 6, the median particle size immediately after preparation and on the 7th day of refrigerated storage was measured with a laser diffraction particle size distribution analyzer “SALD2000A” (Shimadzu Corporation), and the result Are shown in Table 4.

When esterified water-soluble soybean polysaccharide B was used, an emulsion having a smaller median diameter than that when water-soluble soybean polysaccharide Z was used could be prepared at the same rotation speed and stirring time. The effect was exhibited even with short stirring for 20 minutes, and emulsions having median diameters of about 1.4 μm, 1.7 μm, and 2.7 μm were obtained at rotation speeds of 7500 rpm, 5000 rpm, and 2500 rpm, respectively. . With stirring for 60 minutes, a smaller emulsion was obtained, and under the condition of 7500 rpm, an emulsion smaller than 1 μm was obtained. The emulsion did not change the median diameter even after refrigerated storage for 7 days, and was excellent in emulsion stability.

(Examples 10 to 11 and Comparative Examples 7 to 10) Low share preparation of emulsion composition (2)
While adding 8 g of glycerin to 48 g of distilled water and stirring, dissolve 16 g of esterified water-soluble soybean polysaccharide B, water-soluble soybean polysaccharide Z or gum arabic (“Arabic Coal SS” manufactured by Sanei Pharmaceutical Co., Ltd.), 50 The pH was adjusted to 4.0 with a% citric acid solution. Next, lemon oil, MCT (medium-chain fatty acid triglyceride) and sucrose diacetate hexisobutyrate (sucrose diacetic acid hexaisobutyrate) are mixed in advance so that the weight ratio is 2: 3: 5 (specific gravity d 1.010). Was added to each of the above aqueous solutions, and water was further added until the total amount reached 100 g, followed by ice cooling. The ice-cooled solution was stirred with a stirrer “MAZELA Z” (manufactured by Tokyo Rika Kikai Co., Ltd.) for 60 minutes under the condition of 1,000 rpm, and the emulsion compositions of Example 10, Comparative Example 7 and Comparative Example 8 were mixed. Obtained. At that time, in order to confirm the emulsified state in 20 minutes of stirring, a minimum sample necessary for measuring the particle diameter was collected.

Moreover, each emulsion composition of Example 11, Comparative Example 9 and Comparative Example 10 was obtained by the same prescription and procedure as described above except that the number of rotations of stirring was changed to 500 rpm.

For the emulsified compositions of Examples 10 to 11 and Comparative Examples 7 to 10, the median particle diameter immediately after preparation and on the 7th day of refrigerated storage was measured with a laser diffraction particle size distribution analyzer “SALD2000A” (Shimadzu Corporation), and the result Are shown in Table 5.

Even at a lower rotational speed, when using the esterified water-soluble soybean polysaccharide B, an emulsion having a smaller median diameter is prepared than when using the water-soluble soybean polysaccharide Z or gum arabic under the same conditions. I was able to. Even with short stirring for 20 minutes, emulsions having median diameters of about 4.0 μm and 6.4 μm were obtained at rotation speeds of 1,000 rpm and 500 rpm, respectively. When water-soluble soybean polysaccharide Z or gum arabic was used, even when stirring was performed for 60 minutes, it could not be reduced to the median diameter level of the emulsion of esterified water-soluble soybean polysaccharide B.

From the above Examples and Comparative Examples, if an esterified water-soluble soybean polysaccharide is used, it has higher emulsifying power than gum arabic or non-esterified water-soluble soybean polysaccharide, and the resulting emulsion is stable in emulsion. It was confirmed that the property was also high.

According to the esterified water-soluble soybean polysaccharide of the present invention, the emulsifying ability and the emulsion stabilizing ability can be exhibited in a smaller amount than the conventional water-soluble soybean polysaccharide. According to the esterified water-soluble soybean polysaccharide of the present invention, the particle size distribution of the emulsified particles can be reduced without reducing the emulsified particle size without causing an increase in the viscosity of the final product and deterioration of the flavor, It is possible to expand the range of blending into the final product.

In addition, in the production of an emulsion using a conventional polymer emulsifier such as gum arabic, the homogenization treatment with a high-pressure homogenizer is required several times, and the burden on equipment and work is large. According to the esterified water-soluble soybean polysaccharide, it is possible to reduce the particle size by only gentle stirring without performing homogenization with a high-pressure homogenizer. can do.

Furthermore, according to the esterified water-soluble soybean polysaccharide of the present invention, the obtained emulsion, particularly an oil-in-water emulsion, agglomerates or coalesces the emulsion particles by heating, long-term storage or change with time. Can be suppressed, and not only the emulsifying power but also the emulsification stability can be improved.

According to the production method of the present invention, the conventional natural water-soluble soybean polysaccharide can be easily subjected to acetate treatment, the yield is good, the production cost is suppressed, and the production process can be made more efficient.

Claims (15)

An esterified water-soluble soybean polysaccharide having a structure in which one or more of the hydroxyl groups contained in the arabinose residue and / or galactose residue constituting the side chain are acetate esterified. The esterified water-soluble soybean polysaccharide according to claim 1, wherein the acetate esterified structure is contained in an amount of 2% by weight or more in terms of free acetic acid with respect to 100% by weight of the total amount of the esterified water-soluble soybean polysaccharide. The esterified water-soluble structure according to claim 1, wherein the acetate esterified structure is contained in an amount of 2% by weight to 10% by weight in terms of free acetic acid with respect to 100% by weight of the total amount of the esterified water-soluble soybean polysaccharide. Soy polysaccharides. The esterified water-soluble soybean polysaccharide according to claim 1, wherein the acetate esterified structure is contained in an amount of 3% by weight or more in terms of free acetic acid with respect to 100% by weight of the total amount of the esterified water-soluble soybean polysaccharide. The esterified water-soluble structure according to claim 1, wherein the acetate esterified structure is contained in an amount of 3% by weight to 10% by weight in terms of free acetic acid with respect to 100% by weight of the total amount of the esterified water-soluble soybean polysaccharide. Soy polysaccharides. 6. The production method for producing an esterified water-soluble soybean polysaccharide according to any one of claims 1 to 5, comprising a step of subjecting the water-soluble soybean polysaccharide to an acetate esterification treatment. The production method according to claim 6, wherein the acetic esterification treatment is performed by mixing and reacting the water-soluble soybean polysaccharide with acetic anhydride or vinyl acetate. The production method according to claim 6, wherein the mixed amount of acetic anhydride or vinyl acetate is 1 to 50 parts by weight with respect to 100 parts by weight of the dry weight of the water-soluble soybean polysaccharide. The production method according to claim 6, wherein the mixed amount of acetic anhydride or vinyl acetate is 2 to 40 parts by weight with respect to 100 parts by weight of the dry weight of the water-soluble soybean polysaccharide. The production method according to claim 6, wherein the mixed amount of acetic anhydride or vinyl acetate is 3 to 30 parts by weight with respect to 100 parts by weight of the dry weight of the water-soluble soybean polysaccharide. An emulsifier containing the esterified water-soluble soybean polysaccharide according to any one of claims 1 to 5. An oil-in-water emulsion formed using the emulsifier according to claim 11. The oil-in-water emulsion according to claim 12, comprising 0.2 to 5 parts by weight of the esterified water-soluble soybean polysaccharide with respect to 1 part by weight of oil in the oil-in-water emulsion. The oil-in-water emulsion according to claim 12, comprising 0.5 to 3 parts by weight of the esterified water-soluble soybean polysaccharide with respect to 1 part by weight of oil in the oil-in-water emulsion. Use of the esterified water-soluble soybean polysaccharide according to any one of claims 1 to 5 for the preparation of an emulsifier.

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