WO2013058302A1 - 水溶性大豆多糖類およびその製造法 - Google Patents
水溶性大豆多糖類およびその製造法 Download PDFInfo
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- WO2013058302A1 WO2013058302A1 PCT/JP2012/076895 JP2012076895W WO2013058302A1 WO 2013058302 A1 WO2013058302 A1 WO 2013058302A1 JP 2012076895 W JP2012076895 W JP 2012076895W WO 2013058302 A1 WO2013058302 A1 WO 2013058302A1
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- soluble soybean
- soybean polysaccharide
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12G—WINE; PREPARATION THEREOF; ALCOHOLIC BEVERAGES; PREPARATION OF ALCOHOLIC BEVERAGES NOT PROVIDED FOR IN SUBCLASSES C12C OR C12H
- C12G3/00—Preparation of other alcoholic beverages
- C12G3/04—Preparation of other alcoholic beverages by mixing, e.g. for preparation of liqueurs
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/10—Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
Definitions
- the present invention relates to a modified water-soluble soybean polysaccharide.
- it is related with the water-soluble soybean polysaccharide excellent in the emulsification power and the emulsion stabilization power compared with the conventional water-soluble soybean polysaccharide.
- the water-soluble soybean polysaccharide obtained by the present invention is suitable for exerting high emulsifying power and emulsifying stability, characterized by low methyl ester content and moderately containing acetate ester
- the present invention relates to an emulsifier containing a water-soluble soybean polysaccharide as an active ingredient, an oil-in-water emulsion using the emulsifier, and the use of the water-soluble soybean polysaccharide as an emulsifier and an oil-in-water emulsion. .
- the polymer emulsifier maintains the emulsified state without being destroyed even when the emulsion is highly diluted, and also has excellent stability under heating and stability under acidic conditions.
- examples of the polymer emulsifier include gums typified by gum arabic and natural products such as casein, or synthetic products such as acrylates and polyvinyl alcohol. Further, there are octenyl succinic acid crosslinked starches and the like that have been given amphiphilic properties to impart emulsifying power.
- Gum arabic stabilizes oil-in-water (O / W type) emulsions by the sugar chain in gum arabic functioning as a hydrophilic group and the polypeptide bonded to the sugar chain functioning as a hydrophobic group (non-patented) Reference 1).
- Emulsions prepared with gum arabic form a thick hydrophilic layer at the sugar droplet interface, and even when highly diluted, gum arabic is less likely to separate at the oil droplet interface and is excellent for emulsifying fragrances. It is used as an emulsifier.
- Non-patent Document 2 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.
- Patent Document 1 in order to prepare an emulsion having an emulsion particle diameter of less than 1 ⁇ m in diameter, homogenization with a homogenizer is required (Patent Document 1).
- Synthetic polyacrylates and polyvinyl alcohols are excellent in emulsifying power, but have high viscosity, so their usage is often limited.
- modified starches include various modified starches such as etherified starch, esterified starch, crosslinked starch, and grafted starch.
- octenyl succinate esterified starch which is one of esterified starches, is excellent in emulsifying power, but in a highly diluted system, the emulsion stability is extremely low and is not suitable for long-term storage.
- acetate esterified starch in which acetate is bound to starch is also marketed, but it has no emulsion stability and is only used for applications such as aging resistance and viscosity stability.
- Patent Document 2 There has been reported a water-soluble soybean polysaccharide having a high dispersion stability with respect to acidic protein particles and having relatively low viscosity properties by performing demethoxyl treatment (Patent Document 2).
- Patent Document 2 In order to obtain strong emulsifying power, a large amount of addition is necessary, and further improvement is desired.
- the present invention has a small emulsion particle diameter of the oil-in-water emulsion despite the addition of a small amount, the particle size distribution is uniform, and the emulsion particles aggregate due to heating, long-term storage, aging, etc.
- An object of the present invention is to provide a natural polymer emulsifier with improved so-called “emulsifying power” in which unification is suppressed.
- the present invention is surprisingly different from the case where starch is esterified by subjecting water-soluble soybean polysaccharide to demethyl ester treatment and then acetic esterification treatment. It has been found that a strong emulsifying power can be imparted to the water-soluble soybean polysaccharide, and the present invention has been completed.
- the present invention (1) A water-soluble soybean polysaccharide having a methyl ester content with respect to uronic acid of 30% or less and an acetate ester content with respect to water-soluble soybean polysaccharide of 1% by weight or more in terms of free acetic acid. (2) The method for producing a water-soluble soybean polysaccharide according to (1), wherein the water-soluble soybean polysaccharide subjected to the demethyl ester treatment is subjected to an acetate esterification treatment. (3) An emulsifier containing the water-soluble soybean polysaccharide described in (1) as an active ingredient.
- the water-soluble soybean polysaccharide of the present invention can provide emulsifying power and emulsification stabilizing power in a smaller amount than existing water-soluble soybean polysaccharide, has a low viscosity, can reduce the particle size of emulsified particles, and affects the flavor. There is little influence, and the range of blending of the final product is expanded.
- the water-soluble soybean polysaccharide of the present invention is characterized in that the methyl ester content with respect to uronic acid is 30% or less, and the acetate ester content with respect to the water-soluble soybean polysaccharide is 1% by weight or more in terms of free acetic acid. It is a water-soluble soybean polysaccharide. It can also be obtained by subjecting water-soluble soybean polysaccharide to a demethyl ester treatment followed by an acetic esterification treatment.
- a demethyl ester treatment followed by an acetic esterification treatment.
- soybean polysaccharides obtained by various methods can be used.
- a water-soluble soybean polysaccharide as described in Japanese Patent No. 2599477 is used.
- an example of manufacture of water-soluble soybean polysaccharide is shown.
- Soybean is suitable as a raw material for the water-soluble soybean polysaccharide, soy cotyledon is particularly preferable, and so-called okara which is produced as a by-product in the production process of tofu and separated soybean protein is more preferable because it contains abundant polysaccharide.
- okara which is produced as a by-product in the production process of tofu and separated soybean protein is more preferable because it contains abundant polysaccharide.
- a proteolytic enzyme or an alkaline solution in advance, it is possible to extract and remove proteins remaining in the raw materials and concentrate the polysaccharides in the raw materials.
- the water-soluble fraction is preferably removed in advance, and when using okara produced as a by-product in the isolated soybean protein production process, a fat-soluble component is also added to the water-soluble fraction. Since it is removed, it is more preferable as a raw material.
- the solid and the extract are separated by conventional methods such as filtration and centrifugation. At this time, neutralizing the reaction solution after heating to a neutral to weakly acidic range may be suitable for use in foods.
- the extracted filtrate is subjected to the following demethyl ester reaction and acetic esterification reaction as it is or after drying.
- the water-soluble soybean polysaccharide of the present invention is prepared using the water-soluble soybean polysaccharide obtained by the method exemplified above or other methods.
- a water-soluble soybean polysaccharide having a methyl ester content with respect to uronic acid of 30% or less is essential. That is, it is necessary to demethylate the methyl esterified carboxyl group of uronic acid which is a constituent sugar of the water-soluble soybean polysaccharide.
- an acid, an alkali, or an enzyme may be used as the demethyl ester method.
- This demethyl ester treatment is not a problem even before the extraction of the water-soluble soybean polysaccharide, but is preferably performed after the extraction.
- the pH of the water-soluble soybean polysaccharide extract or the aqueous solution of the water-soluble soybean polysaccharide after drying is first adjusted to 9 to 14, preferably using an alkali. Adjust to 11-13.
- alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia.
- the aqueous solution is heated to room temperature or higher, preferably 40 ° C or higher. The higher the treatment pH and treatment temperature, the higher the effect of this step. However, the higher the pH and the higher the heating temperature, the more tend to be colored.
- solid-liquid separation is performed by centrifugation, centrifugal dehydration or pressure filtration.
- This separation step may be carried out in the above alkaline state or at a weak acid to neutral pH.
- the protein in the soybean polysaccharide can be reduced by isoelectric point precipitation of the protein eluted from the raw material by alkali.
- the demethylated water-soluble soybean polysaccharide has a methyl ester content per uronic acid of 30% or less, and preferably 20% or less. If it exceeds 30%, the emulsifying ability may be weakened.
- Acetic acid esterification methods include an aqueous solution of water-soluble soybean polysaccharide or a mixed solution of the aqueous solution and a polar organic solvent such as alcohol or acetone, such as a substance that forms a hydroxyl group and an acetate ester, such as acetic anhydride, vinyl acetate, ice.
- a polar organic solvent such as alcohol or acetone
- an acetate ester such as acetic anhydride, vinyl acetate, ice.
- acetic anhydride and vinyl acetate are desirable from the viewpoint of safety in production.
- safety In the case of glacial acetic acid, safety is high, but reactivity may be weak.
- acetyl chloride there is a danger of reacting violently with water.
- ketene there is a problem that it is difficult to handle because it is a toxic gas.
- the reaction is carried out with stirring while maintaining neutral to alkaline conditions.
- alkali agent added at this time include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and sodium hydrogen carbonate.
- Organic acid salts of alkali metals such as sodium citrate and sodium oxalate, inorganic acid salts of alkali metals such as trisodium phosphate, divalent metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia Etc. can be used. Since the pH of the reaction solution is lowered during the reaction, the above alkaline agent is added as a solid or in the form of a solution in order to maintain the pH.
- the reaction pH is preferably pH 6 to 10, more preferably pH 7 to 9. If the pH is lower than 6, water-soluble soybean polysaccharides may not be sufficiently acetated. Further, even when the pH is higher than 10, water-soluble soybean polysaccharide may be detached and sufficient esterification may not be performed.
- the reaction temperature may be appropriately adjusted to a temperature at which acetic anhydride or vinyl acetate dissolves in the reaction solution, but is preferably 0 ° C. or higher and 60 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower.
- the water-soluble soybean polysaccharide of the present invention is obtained by binding an acetate ester to a polysaccharide.
- the maximum number of acetates to be introduced is determined according to the number of hydroxyl groups in the polysaccharide, the desired effect can be achieved even if those are not introduced into all hydroxyl groups.
- the acetate content relative to the water-soluble soybean polysaccharide is expressed in terms of free acetic acid, it is necessary to contain 1% by weight or more, desirably 2% by weight or more, more desirably 5% by weight. That's it.
- a water-soluble soybean polysaccharide having such a composition is suitable for the intended physical properties. Further, even if it exceeds 10% by weight, there is no significant change in the function, so it is preferably less than 10% by weight.
- Purification treatment The reaction solution containing the obtained water-soluble soybean polysaccharide is subjected to a purification treatment as it is or after neutralization.
- Purification methods include reprecipitation using polar organic solvents such as methanol, ethanol, isopropanol, and acetone, activated carbon treatment, resin adsorption treatment, ultrafiltration method, reverse osmosis method, gel filtration method, dialysis method, ion Examples thereof include an exchange resin method, an electrodialysis method, and an ion exchange membrane method, which can be performed by one method or a combination of two or more methods.
- the use of a reprecipitation method using a polar organic solvent, ultrafiltration, reverse osmosis method, gel filtration method or dialysis method is advantageous because various low molecules can be removed.
- the treatment is preferably performed so that the ash content of the treated polysaccharide is 15% by weight or less, preferably 5 to 10% by weight.
- a water-soluble soybean polysaccharide dried product can be obtained by removing moisture by spray drying, freeze drying, drum drying or the like, with or without concentration.
- titration amount (ml) of 0.1N sodium hydroxide in titration with the end point being red as an indicator.
- V2 is made strongly alkaline by adding sodium hydroxide to the titrated sample aqueous solution so that the final concentration is 0.5 N, and is completely demethylated by heating at 40 ° C. for 20 minutes with stirring.
- a titration amount (ml) of 0.1N sodium hydroxide when titrated in the same manner as V1 by adding hydrochloric acid equivalent to the amount of sodium hydroxide used for demethyl ester.
- the degree of acetic esterification is obtained by hydrolyzing acetic acid ester-bound to water-soluble soybean polysaccharide, quantifying the liberated acetic acid by ion chromatography, and obtaining the acetate content relative to water-soluble soybean polysaccharide by the following formula.
- Acetic acid amount 1.4 ⁇ V2-V1
- V1 is a sample obtained by passing 5 ml of a 0.3 wt% solution of water-soluble soybean polysaccharide, which is a sample, through a filter with a molecular weight of 10,000, and the amount of acetic acid contained in this sample solution is subjected to ion chromatography. Measure by.
- Ion chromatography uses compact IC 861 (manufactured by Metrohm Japan), column is Shodex RS Pak KC-811 ( ⁇ 8mm ⁇ 300mm), 50 °C, eluent is 1mM perchloric acid (flow rate 1ml / min), detector is electric Sodium acetate is used as a conductivity detector and reference material.
- the water-soluble soybean polysaccharide of the present invention has an emulsifying power and a dispersion stability of the emulsion in a small amount, which has been difficult to solve at the conventional technical level. In addition, it can exhibit emulsifying power with only gentle agitation without using a high-pressure homogenizer and other equipment that has a high share of the product. / W type) or an emulsifier for preparing a W / O / W type emulsion.
- water-soluble soybean polysaccharide of the present invention include foods such as soft drinks, milk drinks, soybean drinks, fruit juice drinks, teas, sports drinks, powdered drinks, alcoholic drinks, candy, gummi, Emulsification of confectionery such as jelly and chewing gum, frozen confectionery such as ice cream, dressing, mayonnaise, bakery product, processed fishery product, processed livestock product, retort food, etc., emulsification of oily perfume and emulsification of oily pigment Can be used as an emulsifier. Moreover, it is also effective to add to these food-drinks as an emulsified fragrance
- Non-food applications include shampoos and rinses, hair treatments, hair lotions, waxes and other hair cosmetics, lipsticks, lotions, cleansing creams, shaving foams, facial cleansers, emulsions, hand soaps, foundations, and moisturizers. It can be used as an emulsifier for emulsification of various skin cosmetics such as essence, body shampoo, makeup remover, pharmaceuticals, quasi-drugs, chemicals, feeds, agricultural chemicals, printed materials and the like.
- the 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 mixed with other carriers and additives to make an emulsified preparation.
- the carrier and additive to be used can be appropriately selected depending on the type and use of the product using the emulsifier.
- water-soluble soybean polysaccharide can be used by mixing with a polyhydric alcohol such as glycerin or a saccharide such as dextrin or lactose.
- 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 such as gum arabic.
- the amount added is 0.2 to 5 parts by weight of the water-soluble soybean polysaccharide with respect to 1 part by weight of the hydrophobic substance (oil) contained therein, Preferably 0.5 to 3 parts by weight are added. In the case of a normal emulsified flavor containing 20% by weight of the oil phase, this corresponds to the addition of 4 to 100% by weight of the water-soluble soybean polysaccharide.
- the present invention has a water-soluble soybean polysaccharide in an amount of 0.2 parts by weight or more and less than 0.6 parts by weight, preferably 0.5 parts by weight or more and less than 0.6 parts by weight, with respect to 1 part by weight of oil, and shows a remarkable effect as compared with gum arabic. .
- the emulsified flavor used for the alcoholic drink mentioned later even when using an emulsifier in high concentration, it has a remarkable effect compared with gum arabic.
- Various devices as an emulsifying device for stabilizing the dispersion can be used, and can be appropriately selected according to the particle size and viscosity of the target oil-in-water emulsion.
- 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, or a propeller stirrer.
- a mixer such as a colloid mill, a disper mill, a homomixer, or a propeller stirrer.
- a mixer such as a colloid mill, a disper mill, a homomixer, or a propeller stirrer.
- a mixer such as a colloid mill, a disper mill, a homomixer, or a propeller stirrer.
- a mixer such as a colloid mill, a disper mill, a homomixer, or a propeller stirr
- the hydrophobic substance emulsified in the emulsified fragrance is not particularly limited as long as it is usually used in the dispersed phase of an oil-in-water emulsion.
- Specific oily flavors include, for example, citrus essential oils such as orange, grapefruit, summer tangerine, bergamot, lime, lemon, yuzu, plant essential oils such as flower essential oil, spearmint oil, peppermint oil, onion, garlic, cardamom, cumin, clove.
- Ginger celery, nutmeg, basil, parsley, paprika, black pepper, rosemary, laurel and other essential oils or oleoresin, cola nut extract, coffee extract, cocoa extract, tea extract, spices Oily extracts such as extract and vanilla extract and their oleoresins, eugenol, geraniol, acetic acid, diacetyl, citral, vanillin, ethyl propionate, menthol, butyric acid, limo Flavoring substances such as down, synthetic perfume compounds, oily blended fragrance composition and any mixtures thereof.
- animal and plant oils and fats to be added to the above oily flavor include, for example, olive oil, cacao oil, corn oil, sesame oil, wheat germ oil, rice oil, rice bran oil, safflower oil, soybean oil, camellia oil, rapeseed oil, palm Examples include oil, sunflower oil, cottonseed oil, palm oil, peanut oil, beef tallow, lard, chicken oil, fish oil, butter and the like.
- 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, lauric acid triglyceride and the like, which are used as processed edible oils.
- oil-soluble pigments examples include oil-soluble natural pigments such as anato pigment, chlorophyll, ⁇ -carotene, and paprika pigment.
- oil-soluble vitamins examples include liver oil, vitamin A, vitamin A oil, vitamin B2 butyrate, vitamin D3, natural vitamin E mixture, and the like.
- 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 described above is particularly effective for alcoholic beverages.
- Alcoholic beverages contain 3 to 50% by volume, preferably 20 to 35% by volume of ethyl alcohol, and conventional emulsified fragrances suppress oil floating while maintaining turbidity due to emulsified particles during storage.
- the function is deficient, especially in systems containing 20% by volume or more of ethyl alcohol.
- the emulsified fragrance using the water-soluble soybean polysaccharide of the present invention has a remarkably high emulsification stability when used in these alcoholic beverages as compared with the commonly used gum arabic, and is optimal for alcoholic beverages.
- Example 1-Demethyl ester treatment (pH 12), acetic esterification treatment (20%)- Okara produced during the production of isolated soy protein was used as a raw material, water was added thereto, and the pH was adjusted to 5 with hydrochloric acid. Subsequently, it heated at 125 degreeC for 2 hours using the pressurization pot, and water-soluble soybean polysaccharide was extracted. After extraction, the mixture was centrifuged (5,000 ⁇ g, 10 minutes) to separate into a supernatant and a precipitate mainly containing water-soluble soybean polysaccharide. Sodium hydroxide was added to the supernatant to adjust the pH to 12. Then, it heated at 60 degreeC for 60 minute (s), and the demethylester process was performed.
- the precipitate produced by heating was removed, and the precipitate was removed after adjusting to pH 5.0 with hydrochloric acid. Thereafter, desalting treatment by electrodialysis was performed, and the water-soluble soybean polysaccharide aqueous solution was concentrated to 10 Bx, and adjusted to pH 8.5 with a sodium hydroxide solution. While maintaining the pH at 8.5 with an automatic pH titrator while maintaining 40 ° C, acetic anhydride was added in small portions over a period of 30 minutes to 20% by weight of the solid content, maintaining the pH 8.5 The reaction was further continued for 1 hour. After the reaction, solvent precipitation with ethanol and washing were performed, followed by drying at room temperature to obtain “water-soluble soybean polysaccharide A”. About the obtained water-soluble soybean polysaccharide, it measured by the above-mentioned method about the methyl esterification degree and the amount of acetic acid which carried out ester bond.
- Example 2 (Example 2) -Demethyl ester treatment (pH 11), acetic esterification treatment (10%)-
- water-soluble soybean polysaccharide was extracted and subjected to demethyl ester treatment and acetic esterification treatment.
- the demethyl ester treatment was carried out at a pH of 11, and the acetic esterification treatment was carried out using 10% by weight of acetic anhydride per solid content.
- the obtained “water-soluble soybean polysaccharide B” was analyzed in the same manner as in Example 1.
- Example 3 Demethyl ester treatment (pH 10), acetic esterification treatment (5%)-
- water-soluble soybean polysaccharide was extracted and subjected to demethyl ester treatment and acetic esterification treatment.
- the demethyl ester treatment was carried out at a pH of 10
- the acetic esterification treatment was carried out using 5% by weight of acetic anhydride per solid content.
- the obtained “water-soluble soybean polysaccharide C” was analyzed in the same manner as in Example 1.
- Table 1 shows the results of quality evaluation of the water-soluble soybean polysaccharide solutions obtained in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3.
- 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 / cm2 (14.71). Homogenization was performed twice at MPa) to obtain an emulsified composition (Application Examples 1 to 3, Comparative Application Examples 1 to 3). Each emulsified composition was stored refrigerated, and the particle size immediately after preparation and on the seventh day was measured with a laser diffraction particle size distribution analyzer “SALD2000A” (Shimadzu Corporation). The results are shown in Table 2.
- SALD2000A laser diffraction particle size distribution analyzer
- the particle size is 0.6 ⁇ m or less, and it has better emulsifying power than the conventional water-soluble soybean polysaccharides used in Comparative Application Examples 1 and 2 (water-soluble soybean polysaccharides D and E).
- the particle size was very good at 0.5 ⁇ m or less, and the particle size distribution was uniform. The stability of the emulsified composition was good even after refrigerated storage for 7 days.
- Comparative Application Examples 1 and 2 which are conventional water-soluble soybean polysaccharides
- Comparative Application Example 3 in which only the acetate esterification treatment was performed
- the emulsification characteristics were such that the particle size was about 0.7 ⁇ m. It was bigger than 1-3.
- the change in particle size during the subsequent refrigerated storage for 7 days was small, and the stability of the emulsified compositions in Comparative Application Examples 2 and 3 was particularly good.
- gum arabic in order to obtain a stable emulsified state, when the oil phase is 20% by weight, it is generally necessary to use a high concentration of 12% by weight or more in the system. It was found that the addition of wt% can reduce the particle size of the emulsified particles and has excellent emulsifying power, and also has high emulsifying stability.
- the particle diameter is 0.6 ⁇ m or less, and the conventional water-soluble soybean poly used in Comparative Application Examples 4 to 5 (water-soluble soybean polysaccharides D and E). It had better emulsifying power than saccharides.
- Application Examples 4 to 5 water-soluble soybean polysaccharides A and B
- the application examples 4 to 5 had no oil floating, and the stability of the emulsion composition was good. In the case of the application example 6, only a slight oil floating was observed.
- each emulsion composition was refrigerated and the particle size distribution measuring apparatus “SALD2000A” (Shimadzu Corporation) measured immediately after and on the seventh day. Measured with The summarized results are shown in Table 4.
- water-soluble soybean polysaccharide A has a stronger emulsifying power at the same rotation speed and the same stirring time than water-soluble soybean polysaccharide D, and even in a low-shear preparation without using a high-pressure homogenizer, 20 minutes
- the particle size of 1.5 ⁇ m or less at 7,500 rpm, 2 ⁇ m or less at 5,000 rpm, and 3 ⁇ m or less at 2,500 pm could be maintained.
- the particle size could be maintained at 7500 rpm at 1 ⁇ m or less, 5,000 rpm at 1.5 ⁇ m or less and 2,500 pm at 2 ⁇ m or less even after refrigerated storage for 7 days.
- each emulsion composition was refrigerated and the particle size distribution measuring device “SALD2000A” (Shimadzu Corporation) measured immediately after and on the seventh day. Measured with The summarized results are shown in Table 5.
- water-soluble soybean polysaccharide A has a stronger emulsifying power at the same rotation speed and the same stirring time than water-soluble soybean polysaccharide D, and even in a low-shear preparation without using a high-pressure homogenizer, 20 minutes Refrigerated storage for 7 days with a stirring time of 4 ⁇ m or less at 1,000 rpm and 7 ⁇ m or less at 500 rpm.
- gum arabic had a particle size of around 10 ⁇ m at 1,000 rpm and around 27 ⁇ m at 500 rpm, and its emulsifying power was weak.
- the water-soluble soybean polysaccharide A was able to maintain a particle size of 4 ⁇ m or less at 1,000 rpm and 6 ⁇ m or less at 500 rpm even after refrigerated storage for 7 days with a stirring time of 60 minutes.
- gum arabic took about 6 ⁇ m at 1,000 rpm, but took a long stirring time.
- 500 rpm even if the stirring time is long, it only reaches around 20 ⁇ m, and the emulsifying power is weak.
- the particle size could not be reduced only by stirring with a low share.
- the shampoo of Application Example 13 containing water-soluble soybean polysaccharide A showed a marked improvement in performance due to its smooth hair and good moist feeling.
- the shampoo using the normal gum arabic of Comparative Application Example 15 it is sticky when applied to the skin and hair, and is satisfied with the feel of the skin such as giving a feeling of tension and hardness when dried on the skin and hair. It wasn't possible.
- the emulsified particles can be stabilized with an addition amount smaller than that of ordinary gum arabic. Moreover, the emulsification fragrance
- the existing water-soluble soybean polysaccharide can be dissolved as it is, and can be easily demethylated and acetated in a general tank used in industry, and the yield is also good. Therefore, the manufacturing cost can be suppressed and the efficiency of the manufacturing process can be improved.
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Abstract
Description
Acacia Senegal種に属するアラビアガムを加熱することによって得られる重量平均分子量が90万以上の水溶性改質アラビアガムは、乳化力,乳化安定化力に優れている。しかし、直径1μm未満の乳化粒子径を有する乳化物を調製するには、ホモジナイザーによる均質化が必要である (特許文献1) 。
(1)ウロン酸に対するメチルエステル含量が30%以下であり、かつ水溶性大豆多糖類に対する酢酸エステル含量が、遊離酢酸換算で1重量%以上である、水溶性大豆多糖類。
(2)脱メチルエステル処理が行われた水溶性大豆多糖類に、酢酸エステル化処理を行う、(1)記載の水溶性大豆多糖類の製造法。
(3)有効成分として(1)記載の水溶性大豆多糖類を含有する乳化剤。
(4)(3)記載の乳化剤を用いて、疎水性物質を親水性溶媒に分散安定化する事によって得られる水中油型乳化物。
(5)疎水性物質1重量部に対し、(3)記載の乳化剤を0.3重量部以上7重量部以下使用する、(4)記載の水中油型乳化物。
(6)(1)記載の水溶性大豆多糖類の、乳化剤の調製のための使用。
(7)(1)記載の水溶性大豆多糖類の、エマルジョンの調製のための使用。
である。
以下、本発明の構成につき詳細に説明する。
本発明に原料として使用する水溶性大豆多糖類とは、種々の方法で得られる大豆多糖類を用いることができるが、例えば、特許第2599477号公報に記載された様な水溶性大豆多糖類を用いることができる。以下に、水溶性大豆多糖類の製造の一例を示す。
水溶性大豆多糖類の原料は大豆が適しており、特に大豆子葉部が好ましく、豆腐や分離大豆蛋白質の製造過程で副生する、いわゆるオカラが多糖類を豊富に含むのでより好ましい。また、これらの原料を予め蛋白分解酵素やアルカリ溶液で処理しておくことで、原料中に残存する蛋白質等を抽出除去し、原料中の多糖類を濃縮することができる。なお、原料として豆腐オカラを用いた場合は、水溶性画分が予め除去されており好ましく、分離大豆蛋白質製造工程で副生するオカラを用いた場合は水溶性画分に加えて脂溶性成分も除去されているので、原料として更に好ましい。
上記の原料からの加熱抽出を行う。水溶性大豆多糖類の抽出は水系下で蛋白質の等電点付近である弱酸性域で高温抽出する。抽出温度は100℃ を超えると抽出効率が高く好ましい。100℃未満では、抽出に時間を要し、歩留まりが低下する等実用性の面でも好ましいとは言えず、その上、十分な物性を持つ水溶性大豆多糖類が得られない場合もある。なお、加熱温度の上限は特に規定されないが、極度に高温で行うと副反応が起き、着色し易くなり好ましくない。通常180℃以下、好ましくは150℃以下で行うと良い。
以上に例示された方法、または他の方法により得られた水溶性大豆多糖類を用いて、本発明の水溶性大豆多糖類を調製する。
本発明は、ウロン酸に対するメチルエステル含量が30%以下の水溶性大豆多糖類が必須である。すなわち、水溶性大豆多糖類の構成糖であるウロン酸のメチルエステル化されたカルボキシル基を脱メチルエステルする必要がある。脱メチルエステル法として、酸,アルカリ,もしくは酵素を使用してもよいが、簡便性やコストの点から酸もしくはアルカリを用いることが好ましく、効率の点でアルカリを用いることが最も好ましい。この脱メチルエステル処理は水溶性大豆多糖類の抽出前でも問題ないが、抽出後に行う方が好ましい。
酢酸エステル化方法としては、水溶性大豆多糖類の水溶液または、同水溶液とアルコールやアセトン等の極性有機溶媒との混合溶液に、水酸基と酢酸エステルを形成する物質、例えば無水酢酸,酢酸ビニル,氷酢酸,塩化アセチル,ケテン等を添加して行う。これらの中で、無水酢酸,酢酸ビニルが生産する上での安全性から望ましい。氷酢酸の場合、安全性は高いが、反応性が弱い場合がある。塩化アセチルの場合、水と激しく反応する危険性がある。ケテンの場合、有毒な気体のため、取り扱いが難しい等の課題がある。
反応中も反応溶液のpHは低下するので、pHを維持するために上記のアルカリ剤を固体であるいは溶液の形態で添加する。反応pHは、好ましくはpH6~10、より好ましくはpH7~9である。pH6より低いと水溶性大豆多糖類の酢酸エステル化が十分に行えない場合がある。また、pH10より高くても水溶性大豆多糖類が脱離して、酢酸エステル化が十分に行えない場合がある。また、反応温度は、反応液中で無水酢酸または酢酸ビニルが溶解する温度に適宜調整すれば良いが、好ましくは0℃以上60℃以下、より好ましくは10℃以上50℃以下である。60℃より高い温度になると、無水酢酸の加水分解が早まり、水溶性大豆多糖類と反応しないまま酢酸に分解するものが増える場合がある。一方0℃より低い場合は、水の融点以下であり現実性が低い。
得られた水溶性大豆多糖類を含む反応液はそのまま、または中和後に、必要に応じて精製処理を施す。精製処理する方法として、メタノール,エタノール,イソプロパノール,アセトン等の極性有機溶媒を用いて行う再沈殿法,活性炭処理,樹脂吸着処理,限外濾過法,逆浸透法,ゲル濾過法,透析法,イオン交換樹脂法,電気透析法およびイオン交換膜法等が例示でき、これらの一法又は二法以上の組み合わせにより行うことができる。特に、極性有機溶媒を用いる再沈殿法,限外濾過,逆浸透法,ゲル濾過法あるいは透析法を用いると、種々の低分子をも取り除くことができるので有利である。脱塩を伴う精製処理を行う場合は、処理後の多糖類の灰分が15重量%以下、好ましくは5~10重量%になるように処理するのが好ましい。
通常のペクチンのメチルエステル化度を測定する方法に準じる。即ち、アルカリで脱メチルエステルする前後の試料液を用い、滴定値より以下の計算式によって求める。
メチルエステル化度(DE)= V2/(V1+V2)×100
上式中、V1は、塩酸を含むイソプロピルアルコールを用いて試料のウロン酸をフリーにし、さらにイソプロピルアルコールで洗浄し、塩酸を除去した試料を作成し、この試料水溶液を用いて、フェノールフタレインを指示薬として赤変した点を終点とする滴定における0.1N水酸化ナトリウムの滴定量(ml)である。また、V2は、上記の滴定された試料水溶液に終濃度0.5Nになる様に水酸化ナトリウムを加えて強アルカリ性とし、攪拌下に40℃, 20分間加温して完全に脱メチルエステルし、次いで脱メチルエステルに用いた水酸化ナトリウム量と当量の塩酸を加え、V1と同様にして滴定した時の0.1N水酸化ナトリウムの滴定量(ml)である。
酢酸エステル化の程度は、水溶性大豆多糖類にエステル結合した酢酸を水解し、遊離する酢酸をイオンクロマトグラフィーによって定量し、以下の計算式により水溶性大豆多糖類に対する酢酸エステル含量として求める。
酢酸量=1.4×V2-V1
上中の式、V1は試料である水溶性大豆多糖類の0.3重量%溶液の5mlを分子量1万カットのフィルターに通過させた液を試料とし、この試料溶液に含まれる酢酸量をイオンクロマトグラフィーによって測定する。また、V2は同試料の0.3重量%溶液5mlに、0.5N水酸化ナトリウム1mlを加え、40℃, 20分間、エステル分解処理を行った後、等量の0.5N塩酸1mlを添加する。中和後に分子量1万カットのフィルターに通過させた液を試料とし、この試料溶液に含まれる酢酸量を上と同様に測定する。上記の計算式により、水溶性大豆多糖類に含まれる酢酸量が求められる。
イオンクロマトグラフィーはコンパクトIC 861(メトロームジャパン製)を用い、カラムはShodex RS Pak KC-811(φ8mm×300mm),50℃,溶離液は1mM過塩素酸(流量1ml/min),検出器に電気伝導度検出器,標準物質に酢酸ナトリウムを用いる。
本発明の水溶性大豆多糖類は、従来の技術レベルでは解決が困難であった少ない配合量での乳化力と乳化物の分散安定性を有する。また、高圧ホモゲナイザー等の高度のシェアをかける機器を使用しなくても緩やかな撹拌だけで乳化力を発揮でき、さらに、風味に及ぼす影響が少ないため、従来以上に広い種類の水中油型(O/W型)乳化物またはW/O/W型乳化物を調製するための乳化剤として、使用することができる。
さらに、乳化物の分散安定性に優れるために、医薬品、医薬部外品、化粧品などにおいて、水中油型乳化物またはW/O/W型乳化物を調製するための乳化剤として用いる事が可能である。
非食品用途としては、シャンプー,リンス等の頭髪洗浄料、ヘアトリートメント,ヘアローション,ワックス等の頭髪化粧料、口紅,化粧水,クレンジングクリーム,シェービングフォーム,洗顔料,乳液,ハンドソープ,ファンデーション,保湿エッセンス,ボディーシャンプー,メイク落とし等の各種皮膚用化粧料、医薬品、医薬部外品、化成品、飼料、農薬、印刷物等の、これらの乳化について、乳化剤として用いることができる。
本発明の水溶性大豆多糖類の特に有利な用途として、乳化香料等への使用が例示される。乳化香料は、精製した精油や調合香料を植物油に溶解した疎水性物質からなる相を、アラビアガム等の乳化剤を用いて乳化した水中油型(O/W型)乳化物である。
例えば、乳化香料に本発明の水溶性大豆多糖類を使用する場合、その添加量は、含まれる疎水性物質(油分)1重量部に対して、水溶性大豆多糖類を0.2~5重量部、好ましくは0.5~3重量部を添加する。油相を20重量%含む通常の乳化香料の場合、水溶性大豆多糖類の4~100重量%の添加に相当する。これに対して従来のアラビアガムでは同油相について12重量%を超える量(油分1重量分に対し0.6重量部以上)を添加しなければ、乳化力不十分により乳化粒子径が経時的に増大し、長期の乳化安定性が損なわれる傾向にある。従って、本願発明は油分1重量部に対して、水溶性大豆多糖類を0.2重量部以上0.6重量部未満、好ましくは0.5重量部以上0.6重量部未満で、アラビアガムに比較し顕著な効果を示す。尚、後述するアルコール飲料用に用いる乳化香料の場合は、さらに乳化剤を高濃度に使用する場合でもアラビアガムに比較し顕著な効果を有する。
これら、可食性油性材料はそれぞれ単独で使用することができ、あるいは2種以上の混合物の形で用いることができる。
分離大豆蛋白質製造時に生ずるオカラを原料とし、これに加水し、塩酸にてpHを5に調整した。次いで加圧釜を用いて125℃,2時間加熱し、水溶性大豆多糖類の抽出を行った。抽出後、遠心分離(5,000×g,10分間)し、水溶性大豆多糖類を主に含む上澄と沈澱に分離した。この上澄に水酸化ナトリウムを加え、pH12に調整した。その後、60℃で60分間加熱し、脱メチルエステル処理を行った。加熱して生じた沈殿を取り除き、塩酸を用いて、pH5.0に調整後に沈殿を除去した。その後、電気透析による脱塩処理を行い、水溶性大豆多糖類水溶液が10Bxになるまで濃縮し、水酸化ナトリウム溶液にてpH8.5に調整した。
40℃を保持した状態で、pH自動滴定装置にてpHを8.5に保持しつつ、無水酢酸を対固形分あたり20重量%となるよう少量ずつ、30分かけて添加し、pH8.5を保持したまま、さらに1時間反応させた。反応後、エタノールで溶剤沈殿、洗浄を行い、室温にて乾燥し、「水溶性大豆多糖類A」を得た。得られた水溶性大豆多糖類について、メチルエステル化度およびエステル結合した酢酸量について、前述の方法にて測定した。
実施例1と同様に、水溶性大豆多糖類を抽出し、脱メチルエステル処理および酢酸エステル化処理を行った。但し、脱メチルエステル処理はpHを11とし、酢酸エステル化処理は、無水酢酸を対固形分あたり10重量%用いた。得られた「水溶性大豆多糖類B」について実施例1と同様に分析を行った。
実施例1と同様に、水溶性大豆多糖類を抽出し、脱メチルエステル処理および酢酸エステル化処理を行った。但し、脱メチルエステル処理はpHを10とし、酢酸エステル化処理は、無水酢酸を対固形分あたり5重量%用いた。得られた「水溶性大豆多糖類C」について実施例1と同様に分析を行った。
実施例1と同様に、水溶性大豆多糖類を抽出した。脱メチルエステル処理および酢酸エステル化処理を行うことなく、得られた「水溶性大豆多糖類D」について実施例1と同様に分析を行った。
実施例1と同様に、水溶性大豆多糖類を抽出し、脱メチルエステル処理を行った。酢酸エステル化処理は行わず得られた「水溶性大豆多糖類E」について実施例1と同様に分析を行った。
実施例1と同様に、水溶性大豆多糖類を抽出し、酢酸エステル化処理を行った。但し、酢酸エステル化処理は、無水酢酸を対固形分あたり20重量%用いた。脱メチルエステル処理は行わず得られた「水溶性大豆多糖類F」について実施例1と同様に分析を行った。
上記方法でそれぞれ得られた水溶性大豆多糖類A~Fを使用し、下記手順により各乳化組成物を調製した。
蒸留水100gにグリセリン16.0gを加え、攪拌しながら、水溶性大豆多糖類A~Fを各々21.4g溶解させ、50%クエン酸溶液でpH4.0に調整した。次に、レモンオイル,MCT(中鎖脂肪酸トリグリセライド)及びSucrose diacetate hexaisobutyrate(ショ糖二酢酸六イソ酪酸エステル)を2:3:5の重量比となるよう予め混合したもの(比重d 1.010)を水溶性大豆多糖類A~Fの水溶液に40g添加し、更に全量を200gになるまで水を添加した後に、45℃で保温した。保温した溶液をホモジナイザー「Polytron」(KINEMATICA社製)で、10,000rpmの条件下で10分間予備攪拌し、さらに高圧ホモゲナイザー「ミニラボ8.30H型」(RANNIE社製)を用い、圧力150kgf/cm2(14.71MPa)で2回均質化を行い、乳化組成物を得た(応用例1~3、比較応用例1~3)。各乳化組成物を冷蔵保管し、調製直後,及び7日目の粒子径をレーザ回折式粒度分布測定装置「SALD2000A」(島津製作所)で測定し、結果を表2に示した。
アラビアガムの場合、安定な乳化状態を得るには、油相20重量%の場合一般的に系中12重量%以上の高濃度での使用が必要である事から、水溶性大豆多糖類が10.7重量%の添加で、乳化粒子径を小さくでき乳化力に優れる上に、乳化安定化力も高いことが判った。
応用例1~3および比較応用例1~3の乳化組成物について、酸度とアルコール濃度が高い条件(アルコール飲料のコンクシロップ段階)での評価を行った。水60gにクエン酸1.14g、クエン酸ナトリウム 0.33g、異性化糖11.8gを溶解し、エタノール21mlを加え、水で100mlにメスアップし、コンクシロップとした。このコンクシロップに応用例1~3および比較応用例1~3の乳化組成物を0.3g添加し、室温で保管したものについて、調製直後および3日目の、油浮き,濁度(OD 680),粒子径(レーザ回折式粒度分布測定装置)を測定した(応用例4~6および比較応用例4~6)。結果を表3に示した。
応用例1~3で得られた乳化組成物は、高圧ホモゲナイザーによる150kgf/cm2(14.71MPa)での均質化を2回行う事で、粒子径を0.4~0.7μm程度にまで小さくしている。そこで、実施例1及び比較例1の方法で得られた水溶性大豆多糖類AおよびDを使用し、下記手順により高圧ホモゲナイザーを使用することなく各乳化組成物を調製した。
蒸留水48gにグリセリン8gを加え、攪拌しながら、水溶性大豆多糖類Aまたは水溶性大豆多糖類Dの16gを溶解させ、50重量%クエン酸溶液でpH4.0に調整した。次に、レモンオイル,MCT(中鎖脂肪酸トリグリセライド)及びSucrose diacetate hexaisobutyrate(ショ糖二酢酸六イソ酪酸エステル)を2:3:5の重量比となるよう予め混合したもの(比重d 1.010)を、水溶性大豆多糖類Aまたは水溶性大豆多糖類D溶液に16g添加し、更に全量を100gになるまで水を添加した後に、氷冷した。氷冷した溶液を攪拌機「Polytron」(KINEMATICA社製)で、7,500rpmの条件下で60分間攪拌し、乳化組成物を得た(応用例7,比較応用例7)。その際、攪拌20分時での乳化状態を確認するため、粒子径の測定に必要な最低限のサンプルを採取した。
また、攪拌の回転数を7,500rpm から5,000rpmに変更し、その他の処方は上記と同様にして乳化組成物を得た(応用例8,比較応用例8)。さらに、攪拌の回転数を7,500rpm から2,500rpmに変更し、その他の処方は上記と同様にして乳化組成物を得た(応用例9,比較応用例9)。
応用例7~9で得られる乳化組成物は、攪拌の回転数を2,500rpm ~7,500rpmと比較的少ない回転数でも、2μm以下の粒子径になる事が分かったが、より緩やかな攪拌を行った場合の粒子径を確認してみた。
蒸留水48gにグリセリン8gを加え攪拌しながら、水溶性大豆多糖類A,水溶性大豆多糖類Dまたはアラビアガム(「アラビックコールSS」三栄薬品貿易(株)製)) 16gを溶解させ、50%クエン酸溶液でpH4.0に調整した。次に、レモンオイル,MCT(中鎖脂肪酸トリグリセライド)及びSucrose diacetate hexaisobutyrate(ショ糖二酢酸六イソ酪酸エステル)を2:3:5の重量比となるよう予め混合したもの(比重d 1.010)を、上記の各水溶液に16g添加し、更に全量を100gになるまで水を添加した後に、氷冷した。氷冷した溶液を攪拌機「MAZELA Z」 (東京理化器械株式会社製)で、1,000rpmの条件下で60分間攪拌し、乳化組成物を得た(応用例10、比較応用例10,11)また、攪拌20分時での乳化状態を確認するため、粒子径の測定に必要な最低限のサンプルを採取した。
また、攪拌の回転数を1,000rpm から500rpmに変更し、その他の処方は上記と同様にして乳化組成物を得た(応用例11、比較応用例12,13)。
水溶性大豆多糖類Aは、さらに60分間の攪拌時間で、7日間冷蔵保管しても1,000rpmでは4μm以下、500rpmでは6μm以下の粒子径を維持できた。また、アラビアガムは1,000rpmでは6μm付近になるものの、長い攪拌時間を要した。500rpmでは長い攪拌時間でも20μm付近にまでしかならず、乳化力が弱い。低シェアの攪拌だけでは粒子径を小さく出来なかった。
水溶性大豆多糖類A,水溶性大豆多糖類Dまたは応用例Cで用いたアラビアガムを、表6に示す配合にて、攪拌・混合して水中油型乳化物を作製し、シャンプーを調製した(応用例13、比較応用例14,15)。
水溶性大豆多糖類Aの25部、ヒドロキシプロピルセルロース1部、水74部を攪拌・混合して得られる水中油型乳化物を水酸化ナトリウム水溶液でpH6に調整し、皮膚用化粧料を得た(応用例12)。
また、本発明の製造方法によれば、既存の水溶性大豆多糖類をそのまま溶解し、産業上用いられる一般的なタンク内で容易に脱メチルエステル処理及び酢酸エステル化処理ができ、歩留まりも良いため、製造コストが抑えられ、製造工程の効率化を図る事ができる。
Claims (7)
- ウロン酸に対するメチルエステル含量が30%以下であり、かつ水溶性大豆多糖類に対する酢酸エステル含量が、遊離酢酸換算で1重量%以上である、水溶性大豆多糖類。
- 脱メチルエステル処理が行われた水溶性大豆多糖類に、酢酸エステル化処理を行う、請求項1記載の水溶性大豆多糖類の製造法。
- 有効成分として請求項1記載の水溶性大豆多糖類を含有する乳化剤。
- 請求項3記載の乳化剤を用いて、疎水性物質を親水性溶媒に分散安定化する事によって得られる水中油型乳化物。
- 疎水性物質1重量部に対し、請求項3記載の乳化剤を0.3重量部以上7重量部以下使用する、請求項4記載の水中油型乳化物。
- 請求項1記載の水溶性大豆多糖類の、乳化剤の調製のための使用。
- 請求項1記載の水溶性大豆多糖類の、エマルジョンの調製のための使用。
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CN109354699A (zh) * | 2018-08-01 | 2019-02-19 | 华南理工大学 | 一种基于酯化大豆多糖的水包油型乳液及其制备方法 |
CN110540605A (zh) * | 2019-10-12 | 2019-12-06 | 河南城建学院 | 可溶性大豆多糖的提取和纯化方法 |
CN111333744B (zh) * | 2020-03-30 | 2021-03-26 | 江南大学 | 一种水溶性大豆多糖脱酯的方法及其产品 |
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