WO2006043553A1 - Method for producing modified gum arabic and use thereof - Google Patents

Method for producing modified gum arabic and use thereof Download PDF

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Publication number
WO2006043553A1
WO2006043553A1 PCT/JP2005/019123 JP2005019123W WO2006043553A1 WO 2006043553 A1 WO2006043553 A1 WO 2006043553A1 JP 2005019123 W JP2005019123 W JP 2005019123W WO 2006043553 A1 WO2006043553 A1 WO 2006043553A1
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Prior art keywords
gum arabic
modified
ionizing radiation
modified gum
weight
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PCT/JP2005/019123
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French (fr)
Japanese (ja)
Inventor
Tsuyoshi Katayama
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San-Ei Gen F.F.I., Inc.
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Priority to JP2006543004A priority Critical patent/JPWO2006043553A1/en
Publication of WO2006043553A1 publication Critical patent/WO2006043553A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/28Treatment by wave energy or particle radiation
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/10Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/25Exudates, e.g. gum arabic, gum acacia, gum karaya or tragacanth
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00

Definitions

  • the present invention relates to a method for producing modified gum arabic. More particularly, the present invention relates to a novel process for producing water-soluble modified gum arabic having high dairy stability. The present invention also relates to a water-soluble modified gum arabic prepared by a powerful method and its use.
  • Gum arabic is a natural resin prepared by drying rubber-like exudates obtained from stems and branches of plants belonging to the genus Acacia of leguminous family (Acacia: especially Acacia Senegal and Acacia se). is there. Gum arabic can be dissolved in water to a relatively high concentration, and its aqueous solution has emulsifying properties, emulsion stability, thickening properties, protective colloid properties, and film-forming properties. For this reason, gum arabic has been widely used as an emulsifier, an emulsion stabilizer, a thickener, a binder, a film agent, and the like (see, for example, Non-Patent Document 1).
  • Gum arabic is used in a wide variety of fields. For example, it has long been used as an emulsifier, an emulsion stabilizer, or a thickener in the food field. Therefore, it is a material whose food safety has been confirmed empirically.
  • arabic acid can also be used to remove arabic acid from metal ions.
  • a method of denaturing gum arabic with a loss on drying of 50% by weight or less at 60 to 140 ° C for 30 minutes or longer. See, for example, Patent Document 2
  • a method of modifying gum arabic by heating to 40 ° C or higher in an atmosphere of relative humidity 30 to LOO% see, for example, Patent Document 3
  • a method of modifying gum arabic by heating under the condition of loss on drying of 3% or less for example, see Patent Document 4).
  • gum arabic having high emulsifiability as expected cannot be obtained, and it is not sufficient as a method for modifying gum arabic.
  • the methods (2) to (4) can certainly reduce the quality variation and improve the emulsifying power, but in order to have a sufficient emulsifying effect, heating at a high temperature for a long time is required. Therefore, depending on the processing conditions, coloring and burnt odor (flavoring) may occur, and depending on the application used, the flavor and appearance may be impaired.
  • Non-patent document 1 iNDUSTRIAL GUMS-Polysaccharides and Their Derivatives- ", SE COND EDITION, ACADEMIC PRESS, New York and London, 1973, pp.197-263
  • Non-patent document 2 Williams, PA and Phillips, GO, (2000) in Handbook of Hydrocolloids, Editors Williams, PA and Phillips, GO pp.155—168, Woodhead, London and New York
  • Non-Patent Document 3 "The effects of radiation on carbohydrates” Phillips, CO., Chapter 26 P.1217— 1297, The Carbohydrates Second edition.
  • Non-Patent Document 4 “The effect of sterilizing doses of y-irradiation on the molecular wei ght and emulsification properties of gum ArabicJ Blake, et al, Food Hydrocolloids 1
  • Patent Document 1 Japanese Patent Laid-Open No. 02-049001
  • Patent Document 2 JP 2000-166489 A
  • Patent Document 3 Japanese Patent Application No. 2002-156166
  • Patent Document 4 Japanese Patent Application No. 2003-318958
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-45543
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2003-160602
  • An object of the present invention is to provide a novel method for producing gum arabic that is modified to have high emulsifying power. Furthermore, an object of the present invention is to provide gum arabic excellent in emulsifying power obtained in this way and use of the gum arabic as an emulsifier.
  • the inventors of the present invention have made extensive studies based on the above-mentioned problems.
  • the gum arabic in the aqueous solution is irradiated with ionizing radiation such as ⁇ rays and electron beams. It has been found that the molecular weight of the gum increases and the emulsifying power of gum arabic improves.
  • Item 1 A method for producing modified gum arabic, comprising a step of irradiating an aqueous gum arabic solution with ionizing radiation.
  • Section 2 production method of the modified gum arabic of claim 1, wherein the concentration of gum arabic gum arabic aqueous material is from 15 to 60 weight 0/0.
  • Item 3 The process for producing a modified gum arabic according to Item 1, wherein the ionizing radiation is gamma rays.
  • Item 4 The method for producing modified gum arabic according to Item 1, wherein the ionizing radiation is an electron beam having an acceleration voltage of 0.2 to: LOMeV.
  • Item 5 The method for producing modified gum arabic according to Item 1, wherein the absorbed dose of ionizing radiation is 1 to 50 kGy.
  • Item 7 The method for producing modified gum arabic according to Item 1, wherein the method comprises a drying step after the step of irradiating the gum arabic aqueous solution with ionizing radiation.
  • Item 8 The process for producing a modified gum arabic according to Item 7, wherein the drying step is spray drying or drum drying.
  • Item 9 A modified Arabicum obtained by the production method according to any one of Items 1 to 7.
  • Item 10 An emulsifier comprising the modified gum arabic described in Item 9 as an active ingredient.
  • Item 11 A method for preparing an emulsified composition using the modified gum arabic described in Item 9 as an emulsifier.
  • Emulsion composition strength The method for preparing an emulsion composition according to Item 11, which is oZw type emulsion or wZoZw type emulsion.
  • Item 13 Using modified gum arabic as described in Item 9 as an emulsifier, essential oil, oily fragrance, oily pigment, oil-soluble vitamin, polyunsaturated fatty acid, animal and vegetable oil, sucrose acetate isobutyrate ester, and medium Item 12.
  • the method for preparing an emulsified composition according to Item 11, comprising a step of dispersing and stabilizing at least one selected hydrophobic substance in a hydrophilic solvent.
  • Item 16 The emulsified composition according to Item 14, which is a food or drink.
  • a modified Arabica gum excellent in emulsifying power is obtained by irradiating a natural (unmodified) gum arabic aqueous solution used as a raw material with ionizing radiation.
  • a natural (unmodified) gum arabic aqueous solution used as a raw material with ionizing radiation can be obtained.
  • the present invention adopts the above-mentioned treatment method, which is a problem in the conventionally known reforming method by heating, and efficiently prevents the agglomeration due to coloring or adhesion during the treatment. This is a useful method by which gum arabic having good emulsifying power can be obtained.
  • the modified gum arabic of the present invention thus prepared can be suitably used for emulsification of various hydrophobic substances such as essential oils, oil-based pigments, oil-based fragrances, and oil-soluble vitamins.
  • the emulsion (emulsion composition) prepared using the modified gum arabic of the present invention has a uniform particle size distribution compared to the emulsion prepared using natural gum arabic commonly used, and It is extremely stable because the emulsion particles are agglomerated or coalesced due to abuse such as heating, long-term storage, or aging, and the particles are deteriorated by coalescence.
  • FIG. 1 Changes in molecular weight of sample 1 (gum arabic powder) and samples 2 to 5 (20, 35, 50, and 60% by weight aqueous gum arabic gum) when irradiated with an electron beam
  • the present invention is a method for modifying gum arabic to have high emulsifying power, in other words, a method for producing gum arabic obtained by modifying gum arabic to have high emulsifying power.
  • the method of the present invention can be carried out by irradiating an aqueous gum arabic solution with ionizing radiation.
  • the “emulsifying power” as used in the present invention includes both the emulsifying power during the emulsification treatment and its stability over time.
  • emulsification means the former characteristic
  • emulsification stability means “the latter characteristic”.
  • gum arabic used as a modification target is Acacia Senegal or Acacia seval belonging to the genus Acacia which is a leguminous plant. It is a natural exudate obtained from the trunk and branch strength of these genus plants. Alternatively, it may be subjected to further purification treatment, desalting treatment, or processing such as pulverization or dry spraying.
  • these raw materials are simply referred to as “gum arabic” t, or “natural gum arabic” or “unmodified gum arabic” in the sense of being distinguished from the modified gum arabic of the present invention.
  • Natural gum arabic (A. senegal species) is usually found in North Africa and Ethiopian powers in Senegal and countries in West Africa (Ethiopia, Sudan, Seneganore, Nigeria, -Gier, Ghana), Kenya, Kenya and other East African countries In the Saharan region of Africa, the basin region of the Nile tributary, but in the present invention, it may be derived from any production region without questioning its origin.
  • natural gum arabic can be obtained in the form of a lump, ball, coarsely pulverized product, granule, granule, or powder (including spray-dried powder).
  • V and misalignment can be used as the gum arabic to be modified.
  • Aqueous gum arabic solution to be irradiated with ionizing radiation is prepared by dissolving these various forms of natural Arabica gum (unmodified gum arabic) in water.
  • Water to be used is not particularly limited, and may be tap water, distilled water, or ion exchange water. Ion exchange water is preferable.
  • the concentration of gum arabic in the aqueous gum arabic solution varies depending on the type of gum arabic used and the amount of the gum arabic, and a force in the range of usually 15 to 60% by weight can also be selected. 30-55 is properly preferred weight 0/0, more preferably 35 to 50 wt%. If the concentration of gum arabic in the gum arabic aqueous solution is lower than 15% by weight, the modification tends not to proceed sufficiently even when irradiated with ionizing radiation, making it difficult to improve efficiently. On the other hand, when the gum arabia gum concentration exceeds 60% by weight, it becomes difficult to evenly dissolve gum arabic in water evenly. Tends to be lost.
  • the gum arabic aqueous solution is prepared by dissolving gum arabic in water that has been heated as necessary, and then removing insoluble matter and mixed waste by centrifugation or filter press filtration. It is preferred (solid-liquid separation).
  • Irradiation with ionizing radiation can be performed in a state where the aqueous gum arabic solution thus prepared is placed in an arbitrary container depending on the type of ionizing radiation to be irradiated.
  • the gum arabic aqueous solution has a low fluidity, such as a paste, it is possible to irradiate it with ionizing radiation immediately without placing it in a container.
  • the type of ionizing radiation is not particularly limited, and any of ionizing radiation (y-ray, electron beam, X-ray) can be used. Gamma rays or electron beams are preferred.
  • ⁇ -rays Since ⁇ -rays have a larger transmission power than electron beams, they are suitable for irradiating a thick sample. Moreover, as long as ⁇ -rays are transmitted, there is an advantage that the type of container used for storing the sample is not limited. For example, with ⁇ -rays, it is possible to irradiate a large amount of sample in a large drum can stainless steel container, so that a large amount of Arabic aqueous solution can be irradiated (modified) at once. it can.
  • the ⁇ -ray irradiation includes irradiation using cesium 137 as a radioisotope and irradiation using conoret 60, and ⁇ -ray irradiation using cobalt 60 is preferable.
  • cobalt 60 when used in a sealed capsule made of stainless steel, it can be handled safely and easily without problems such as environmental pollution. Compared to the default 60, it has the disadvantages that it is not easy to handle safely and the dose per unit time, that is, the dose rate is low and the irradiation efficiency is poor!
  • electron beams do not use radioisotopes such as cobalt 60 and cesium 137 like ⁇ -rays, so shielding devices may be relatively simple, which is preferable in terms of safety and work.
  • a source of radiation In addition, electron beam irradiation is said to have a high treatment capacity due to a high dose per unit time, that is, a dose rate.
  • the transmission power of electron beams varies depending on the acceleration voltage, the transmission power is generally smaller than that of gamma rays. For this reason, it is preferable to adjust the irradiation sample (gum arabic gum aqueous solution) according to the transmission power (electron beam energy) of the electron beam used.
  • the irradiation sample for example, when using a high energy electron beam of about lOMeV, the thickness of the irradiated sample should be several mn! Even when the thickness is adjusted to be relatively thick, such as about 3 cm, uniform irradiation is possible.
  • IMeV low-energy electron beam of IMeV or less, it is preferable to adjust the sample thickness to 3 mm or less in order to irradiate uniformly.
  • the electron beam irradiation is performed with a sample to be irradiated having a small thickness, or a sample whose thickness can be adjusted (for example, powder, fluid, liquid, thinnable solid). If so, it is a more preferable irradiation method from the viewpoint of economical and industrial production because it has a large processing capacity and can be processed in large quantities as described above.
  • the electron beam irradiation is performed using an electron accelerator.
  • the acceleration voltage is not particularly limited, but is usually about 0.2 to about LOMeV, preferably about 0.3 to 8 MeV.
  • a sample is usually filled in a polyethylene bag and the thickness thereof is adjusted according to the energy of the electron beam.
  • the irradiation sample (gum arabic gum aqueous solution) is filled in a polyethylene bag, and spreads thinly and irradiates it as uniformly as possible.
  • IMeV low energy electron beam of IMeV or less
  • the thickness of the irradiated sample is limited, so in order to efficiently process a large number of samples, the irradiated sample is spread thinly and moved on the conveyor. Irradiation is preferred.
  • a method of irradiating the double-sided force is also preferably used.
  • these irradiation conditions are selected and used according to various factors such as the fluidity and specific gravity of the gum arabic aqueous solution to be irradiated, or the packaging material (container) that accommodates it. Togashi.
  • a gum arabic solution having fluidity of 15 to 50% by weight of gum arabic is used as an irradiation sample
  • cobalt 60 is used. It is preferable to use ionizing radiation with relatively high transmission power, such as gamma rays and high-energy electron beams of about lOMeV.
  • ionizing radiation with relatively high transmission power such as gamma rays and high-energy electron beams of about lOMeV.
  • a suitable irradiation method when ⁇ -rays are irradiated using cobalt 60, a method of irradiating a gum arabic gum aqueous solution in a sealable drum can, an Atron can, or a stainless steel container can be exemplified.
  • the gum arabic aqueous solution is sealed in an aluminum or polyethylene container and the thickness is several mn! The method of adjusting the irradiation to about 3 cm or less can be mentioned.
  • ionizing radiation with relatively high transmission power, such as gamma rays using cobalt 60 and high-energy electron beams of about lOMeV.
  • a polyethylene sheet is laid on the conveyor, and an appropriate thickness (preferably about several mn! To 3 cm or less) is used on the top of the sheet.
  • the paste-like gum arabic aqueous solution adjusted to 1 can be spread and irradiated. This makes it possible to irradiate the gum arabic aqueous solution with an electron beam continuously and in large quantities. It is also possible to put a paste-like gum arabic aqueous solution in a polyethylene bag and adjust the thickness as described above for irradiation.
  • the absorbed dose of ionizing radiation applied to the gum arabic aqueous solution is not particularly limited as long as the effect of the present invention is obtained.
  • a suitable absorbed dose varies depending on the concentration of gum arabic in the gum arabic aqueous solution, a range power of usually 1 to 50 kGy can be appropriately selected and used.
  • the absorbed dose is preferably in the range of 10-50 kGy, more preferably in the range of 20-40 kGy.
  • the polymerization rate by ionizing radiation tends to be high.
  • the preferred absorbed dose range is 3-30 kGy, more preferably 10-25 kGy.
  • the absorbed dose of ionizing radiation can be measured according to a standard method. Specifically, for example, a measurement method using a CTA dosimeter (for example, FTR-125, Fuji Photo Film Co. Ltd, etc.) calibrated with a Fricke dosimeter can be exemplified.
  • the gum arabic aqueous solution irradiated with ionizing radiation can be dried as it is or appropriately diluted with water and then dried by a conventional method such as spray drying, drum drying, freeze drying, etc. It can also be provided as quality gum arabic.
  • a drying method using a drying apparatus such as a vacuum dryer or a vacuum dryer can also be used as an industrial drying method. In these devices, the pressure in the container containing the gum arabic aqueous solution can be lowered by a water pump or a vacuum pump, and the content (gum arabic gum aqueous solution) can be uniformly mixed with a screw or the like.
  • the apparatus can be equipped with an apparatus that can heat the contents by introducing steam into the jacket outside the container, operations such as drying (moisture removal), mixing, and heating are performed once. Can be done. Further, according to the apparatus, after the heating is completed, the contents can be rapidly cooled by mixing the contents while passing cooling water through the jacket outside the container.
  • these specific devices are: Ribocon (conical ribbon vacuum dryer (RM-VD type): manufactured by Okawara Seisakusho Co., Ltd.), vacuum type Nautamixa NXV type (manufactured by Hosokawa Micron Co., Ltd.), planetary motion type cone Examples include a type mixing dryer SV mixer (manufactured by Shinko Pantech Co., Ltd.).
  • the form of the modified gum arabic prepared by the drying treatment is not particularly limited, and examples thereof include powder, granules and granules.
  • emulsifying power Particularly preferred from the viewpoint of emulsion stability are those having a weight average molecular weight of 1 million or more.
  • the present invention can also be referred to as a method of modifying gum arabic so as to increase emulsifying power, particularly emulsification stability, in a state where coloring is reduced.
  • the modified gum arabic obtained by the production method of the present invention is suitable as an emulsifier for foods, cosmetics, pharmaceuticals or quasi-drugs, particularly products having a great influence on the quality of color and odor.
  • the method for producing the modified gum arabic of the present invention further includes various products (food, aroma, etc.) using the modified gum arabic as an emulsifier. It may be provided with processing steps necessary for application to cosmetics, pharmaceuticals or quasi-drugs!
  • a treatment step for preparing a suitable state (composition or form) as an emulsifier may be provided.
  • the modified gum arabic prepared by the above method can be clearly distinguished from unmodified gum arabic (natural gum arabic) used as a raw material with high emulsifying power.
  • the emulsifying power of an emulsifier is evaluated to be superior as the average particle size of the prepared emulsion is smaller and the particle size is more stably maintained over time (“Emulsification with Arabic gum”).
  • OZW Emulsion by turbidity ratio method ", Pharmaceutical Journal, 112 (12), 90 6-913, (1992)).
  • the modified gum arabic of the present invention is suitably used as an emulsifier, particularly as an emulsifier for products that can be taken orally, particularly in the field of food, pharmaceuticals, quasi drugs, or cosmetics. be able to.
  • beverages, powdered beverages, desserts, chewing gum It can be suitably used as an emulsifier for dairy products such as foodstuffs, tablet confectionery, snack confectionery, processed fishery products, processed livestock products, and retort foods, emulsified oily fragrances, and emulsified oily pigments.
  • the modified gum arabic can be used as an emulsifier in the state of an aqueous solution as it is after irradiation with ionizing radiation or in the solid state after drying (for example, in the form of particles or powder).
  • other carriers and additives can be blended to prepare an emulsifier.
  • the carrier or additive used depends on the type of product using the emulsifier (for example, food, medicine, quasi-drug, or cosmetic) and its use.
  • the proportion of the modified gum arabic contained in the emulsifier is not limited, but at least the lower limit is
  • the content be 5% by weight or more, preferably 10% by weight or more.
  • the upper limit is not particularly limited as long as it is less than 100% by weight! ,.
  • the present invention also provides a method for preparing an emulsion (emulsified composition) using the modified gum arabic as an emulsifier.
  • the emulsion can be prepared by dispersing and stabilizing a hydrophobic substance (dispersoid) in a hydrophilic solvent (dispersion medium) using the modified gum arabic as an emulsifier.
  • emulsion emulsified composition
  • examples of emulsion (emulsified composition) include oil-in-water (oZw) type and wZoZw type emulsion.
  • the hydrophobic substance to be emulsified here is not particularly limited as long as it is ordinarily provided in emulsion form, but is preferably in the food, pharmaceutical, quasi-drug or cosmetic field. And edible hydrophobic substances that can be used orally.
  • various essential oils obtained from basic plants such as citrus plants such as orange, lime, lemon and grapefruit, and basic plant powers such as pepper, cinnamon and ginger.
  • Oleoresin and jasmine obtained by oleoresin method
  • Oils such as absolute, obtained from the basic plant such as rose and rose, etc., other synthetic fragrance compounds, and oil-based compound fragrance compositions
  • vitamins A, D Fat-soluble vitamins such as E and K
  • Polyunsaturated fatty acids such as docosahexaenoic acid, eicosapentaenoic acid, and ⁇ linolenic acid
  • Animal and vegetable oils such as soybean oil, rapeseed oil, corn oil and fish oil
  • SAIB Sucrose Acetate isobutyrate : Sucrose acetate isobutyrate
  • processed food oils such as
  • the method of preparing the emulsion using the modified gum arabic is not particularly limited, and the hydrophobic substance and the hydrophilic solvent are added according to a conventional method for preparing oil-in-water (OZW) type emulsion or WZOZW type emulsion.
  • OZW oil-in-water
  • WZOZW WZOZW type emulsion
  • it can be carried out by mechanically stirring and emulsifying using a homogenizer, high-pressure jet or the like. More specifically, the following method can be illustrated.
  • the modified gum arabic is dissolved in a hydrophilic solvent such as water, and if necessary, impurities are removed by an appropriate solid-liquid separation means such as centrifugation or filtration using a filter press.
  • a modified gum arabic aqueous solution is prepared.
  • a desired hydrophobic substance used as a dispersoid for example, oil and fat, or a mixed solution in which a fragrance or a pigment is previously dissolved in oil or fat
  • the specific gravity may be adjusted with a specific gravity adjusting agent such as SAIB as necessary.
  • the obtained pre-emulsified mixture is emulsified using an emulsifier.
  • an emulsified fragrance or an emulsified dye is prepared using an oily fragrance or an oily dye as the hydrophobic substance
  • a mixed solution in which the oily fragrance or the oily dye is previously dissolved in an oil or fat is used as the hydrophobic substance. It is preferable. As a result, the emulsification can be further stabilized and the volatilization of the components can be prevented.
  • Oils and fats that dissolve oily fragrances and oily pigments are not particularly limited, but usually, medium chain triglycerides (triglycerides having 6 to 12 carbon atoms) and vegetable oils such as corn oil, safflower oil, or soybean oil are used. Can be used.
  • the emulsifier used for emulsification can be appropriately selected according to the size of the target emulsion particles, the viscosity of the sample, and the like, which are not particularly limited.
  • an emulsifier such as a nanomizer or disperser mill or colloid mill can be used.
  • a hydrophobic substance is added to a hydrophilic solvent under stirring, and the mixture is stirred and pre-emulsified to prepare emulsified particles having a particle size of about 2 to 5 ⁇ m. And then homogenize Fine and uniform particles (e.g., average particle size) using an emulsifier such as
  • the dye crystals are first mixed with an appropriate oil and fat at high temperature and dissolved, and then added to a hydrophilic solvent.
  • the ratio of the modified gum arabic used is not particularly limited, but the ratio in 100% by weight of emulsion usually includes 5 to 20% by weight.
  • the emulsion (emulsion composition) prepared using the modified gum arabic has a particle size smaller than that of the emulsion prepared using ordinary natural gum arabic [unmodified gum arabic].
  • the distribution is uniform, and the emulsion particles are agglomerated or coalesced by heating and long-term storage, etc., and the deterioration of the particles is significantly suppressed, providing high stability over time.
  • the food made using the emulsion prepared using the modified gum arabic is not particularly limited.
  • milk drink, lactic acid bacteria drink, carbonated drink, fruit drink, powder drink, sports drink, tea Beverages such as beverages and green tea beverages
  • puddings such as custard pudding and milk pudding
  • desserts such as jelly, bavaroa and yogurt
  • frozen confectionery such as milk ice cream and ice candy
  • Coated chocolate such as marble chocolate, chocolate such as melon chocolate, etc .
  • caramels such as node candy, soft candy, caramel, and drop
  • node biscuits, cookies, and okaki Baked goods such as corn soup Sauces such as pork and potage soup, dressings, ketchup, mayonnaise, sauce, sauces and other sauces
  • processed meat products such as sausages, sausages and grilled pork
  • fish paste products such as fish sausages and salmon
  • butter, margarine, Fats and oils such as cheese Examples of processed foods such as products.
  • the present invention will be described with reference to test examples and examples. However, the present invention is not limited to these examples. It is not limited to such as.
  • the absorbed dose was measured using a CTA dosimeter (FTR-125, Fuji Photo Film Co. Ltd) calibrated with a Fricke dosimeter.
  • Example 1 Spray-dried powdered gum arabic [S ⁇ M, MW 600,000, loss on drying 7.0%] (Sample 1) in a 0.04 mm thick polyethylene bag (New Pack G-8, Produced by Nippon Stock Co., Ltd. (140 mm wide x 200 mm long), put 50 g so that the thickness of the sample is about 3 mm, make it uniform, and use a vandegraph electron accelerator to accelerate voltage 0.8 MeV, dose rate 60 Electron beams were irradiated with absorbed doses of 10, 20, 30, and 50 kGy under the conditions of OkGyZhr (electron beam irradiation sample 1).
  • a spray-dried powdered gum arabic (A.Smigsal, MW60 ten thousand, dried down weight 7.0%) was blended in ion-exchanged water, the concentration of gum arabic 20 weight 0
  • An aqueous solution of gum arabic was prepared so as to be / 0 (sample 2), 35 wt% (sample 3), 50 wt% (sample 4), and 60 wt% (sample 5).
  • 75 g of the sample water solution is placed in a polyethylene bag with a thickness of 0.04 mm (manufactured by Nippon Co., Ltd .: 140 mm wide x 200 mm long) so that the thickness is about 3 mm.
  • an electron beam is absorbed with an absorbed dose of 10, 20, 30, and 50 kGy for each sample (samples 2 to 5) under the conditions of an acceleration voltage of 0.8 MeV and a dose rate of 600 kGyZhr. Each was irradiated (electron beam irradiated samples 2 to 5).
  • the weight average molecular weight of gum arabic is measured by gel filtration chromatography with three detectors connected online, a light scattering tongue (MALLS) detector, a refractive index (RI) detector, and a UV detector.
  • MALLS light scattering tongue
  • RI refractive index
  • UV detector a UV detector
  • MALL S light scattering
  • the molecular weight can be detected by the detector, the weight (composition ratio) of each component can be detected by the refractive index (RI) detector, and the protein can be detected by the UV detector.
  • the molecular weight and composition of the analytical component can be determined without any problem. Its detailed principles and features are described in Idris, OHM, Williams, PA, Phillips, GO; Food Hydrocolloids, 12,375-388 (1998) J.
  • Sample preparation After the analysis sample (electron beam irradiated sample) is diluted with the elution solvent (0.2 M NaCl), measure the solution from which insolubles have been removed with a 0.45 m cellulose acetate membrane filter.
  • the elution solvent 0.2 M NaCl
  • MALLS multi angle laser light scattering: DAWN EOS (Wyatt Technology, USA), 2) RI (refractive index), 3) UV (absorption at 214 nm).
  • the entire peak on the chromatogram obtained by the RI detector (when the rising edge of the RI chart from the baseline of the chart starts and descends and the intersection with the baseline is the end point)
  • the starting force also means the RI chart part to the end point.)
  • the molecular weight determined by weight conversion was defined as the “weight average molecular weight”. As the emulsifying power increases, the “weight average molecular weight” also increases, which can be used as an index for evaluating emulsifiability.
  • Electron beam irradiated sample 1 90 g of ion exchange water was added to sample lOg and mixed well to prepare a 10% by weight aqueous solution of gum arabic. Electron beam irradiated samples 2 to 5 were prepared using ion-exchanged water so that the gum arabic concentration was 10% by weight.
  • Each electron beam irradiation sample prepared as a 10% by weight aqueous solution as described above was placed in a 100 ml screw tube, and a B-type viscometer (BM type, Tokimec Co., Ltd.) at 20 ° C. ), The viscosity (mPa's) was measured under the conditions of rotor No. 1 and rotation speed of 60 rpm. (For samples that cannot be measured with rotor No. 1, use rotor No. 2 with the same rotation speed of 60 rpm.) Viscosity (mPa ⁇ s) was measured under the conditions).
  • Table 1 shows the results of the above measurements.
  • Figures 1, 2 and 3 show the changes in molecular weight, viscosity, and coloring degree when each sample (Samples 1-5) was irradiated with an electron beam of each absorbed dose (0-50 kGy).
  • Attachment Caro combined mixed ion exchange water 300g into ⁇ -ray irradiation was 35 weight 0/0 arabic gum aqueous was 500 g, while stirring the solution, 0.
  • D. is a medium-chain triglyceride (octanoic 'decanoic acid triglyceride) 0 (Trade name, manufactured by Nisshin Oillio Co., Ltd.)
  • the average particle size m) immediately after emulsification and after storage at 60 ° C for 3 days was measured using a particle size distribution analyzer SALD-1100 (laser diffraction type, manufactured by Shimadzu Corporation). Use to measure.
  • SALD-1100 laser diffraction type, manufactured by Shimadzu Corporation.
  • the emulsifying power of an emulsifier is equal to the level of the emulsion to be prepared. It is estimated that the smaller the average particle size and the more stable the particle size over time, the better it will be (“Study by the turbidity ratio method of o / w emulsion emulsified with gum arabic”). "Pharmacological Journal, 112 (12) 906-913, (1992)).
  • Emulsification stability was also evaluated by the difference in average particle size immediately after emulsification and after storage at 60 ° C for 3 mm.
  • Table 3 shows the evaluation results of emulsifying power.
  • the stability of emulsion over time is the difference between the average particle diameter (a) of emulsion just after emulsification and the average particle diameter (b) of emulsion after accelerated test (stored at 60 ° C for 3 days).
  • (b— a) Force can also be judged. The smaller the change in the average particle size of the emulsion, the better the stability with time (emulsification stability).
  • Example 1 8—Strength Rotin Emulsified Formulation (Emulsified Dye Formulation)
  • the modified gum arabic 170g was dissolved in water 680 g, it was manufactured by adjusting the aqueous gum arabic solution of 20 weight 0/0. This was used as a wrinkle preparation, and medium chain triglyceride (octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)) 100 g was mixed and heated at 150 ° C. to dissolve, and the mixed solution was added and mixed with stirring.
  • medium chain triglyceride octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)
  • Example 2 Orange emulsified flavor (emulsified flavor)
  • the modified gum arabic 170g was dissolved in water 680 g, it was manufactured by adjusting the aqueous gum arabic solution of 20 weight 0/0. Using this as an emulsifier, it was prepared by mixing in advance 20 g of orange fragrance and 130 g of medium chain triglyceride (octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)) at room temperature. The previously mixed liquid was added and mixed with stirring. This is emulsified with a homogenizer (APV GAULIN) (with a pressure of 4.4 MPa (450 kg / cm 2 )). The orange emulsified fragrance was prepared as an emulsified fragrance.
  • AAV GAULIN homogenizer
  • the modified gum arabic 170g was dissolved in water 680 g, it was manufactured by adjusting the aqueous gum arabic solution of 20 weight 0/0. Using this as an emulsifier, a mixture of 50 g of fish oil containing 20% by weight of DHA and medium chain triglyceride (octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)) lOOg was added in advance to 80 °. The mixture prepared by heating to C and mixing was added and mixed by stirring.
  • a homogenizer manufactured by APV GAULIN
  • APV GAULIN homogenizer at a pressure of 4.4 MPa (450 kg / cm 2 ) four times

Abstract

Disclosed is a method for efficiently enhancing emulsification properties of a gum arabic. Also disclosed is a method for producing a gum arabic so modified as to have high emulsification properties. Such a gum arabic is obtained by irradiating an aqueous gum arabic solution with ionizing radiation.

Description

明 細 書  Specification
改質アラビアガムの製法及びその用途  Process for producing modified gum arabic and its use
技術分野  Technical field
[0001] 本発明は、改質アラビアガムの製造方法に関する。より詳細には、本発明は高い乳 化安定性を有する水溶性の改質アラビアガムを製造する新規な方法に関する。また 、本発明は力かる方法によって調製される水溶性の改質アラビアガム、及びその用 途に関する。  [0001] The present invention relates to a method for producing modified gum arabic. More particularly, the present invention relates to a novel process for producing water-soluble modified gum arabic having high dairy stability. The present invention also relates to a water-soluble modified gum arabic prepared by a powerful method and its use.
背景技術  Background art
[0002] アラビアガムは、マメ科アカシア属に属する植物(アカシア:特に Acacia Senegal及 び Acacia se )の幹や枝カゝら得られるゴム状の滲出液を乾燥して調製される天然榭 脂である。アラビアガムは水に比較的高濃度まで溶解することができ、またその水溶 液は乳化性、乳化安定性、増粘性、保護コロイド性、及びフィルム形成性を有する。 このため、アラビアガムは、従来から広く乳化剤、乳化安定剤、増粘剤、結合材及び 皮膜剤などとして利用されている (例えば、非特許文献 1等参照)。アラビアガムの利 用分野は多岐に亘つており、例えば食品分野においても、乳化剤、乳化安定剤、ま たは増粘剤などとして古くから使用されている。ゆえに、食への安全性も経験的に確 認されている素材である。  [0002] Gum arabic is a natural resin prepared by drying rubber-like exudates obtained from stems and branches of plants belonging to the genus Acacia of leguminous family (Acacia: especially Acacia Senegal and Acacia se). is there. Gum arabic can be dissolved in water to a relatively high concentration, and its aqueous solution has emulsifying properties, emulsion stability, thickening properties, protective colloid properties, and film-forming properties. For this reason, gum arabic has been widely used as an emulsifier, an emulsion stabilizer, a thickener, a binder, a film agent, and the like (see, for example, Non-Patent Document 1). Gum arabic is used in a wide variety of fields. For example, it has long been used as an emulsifier, an emulsion stabilizer, or a thickener in the food field. Therefore, it is a material whose food safety has been confirmed empirically.
[0003] し力しながら、アラビアガムは、アフリカのサハラ地帯に点在する様々な国から採取 されるため、各生産地における土壌や気候の相違に基づいて採取される天然のァラ ビアガムの分子量と分子量分布には非常に大きなバラツキがある。また、このバラッ キは、アラビアガムを採取する榭の種類ゃ榭齢の相違、並びに収穫時期の違いによ つても生じる。それ故に、天然のアラビアガムを用いて乳化剤、乳化安定剤、または 増粘剤を調製する場合には、原料とする天然アラビアガムのノ ツキに起因して一定 の品質のものが得られな ヽと ヽぅ問題がある (例えば、非特許文献 2参照)。  [0003] However, because gum arabic is collected from various countries scattered in the Saharan region of Africa, natural gum arabia gum is collected based on differences in soil and climate in each production area. There are very large variations in molecular weight and molecular weight distribution. This variation also occurs due to differences in age and harvest time of the gums from which gum arabic is collected. Therefore, when preparing an emulsifier, an emulsion stabilizer, or a thickener using natural gum arabic, a product of a certain quality cannot be obtained due to the lack of natural gum arabic as a raw material. There is a problem with this (for example, see Non-Patent Document 2).
[0004] また、アラビアガムは気候などの自然要因や生産地の状況などにより生産量が大き く変動することから、不作の年にはアラビアガムの価格は暴騰する。このため、できる だけ少量で乳化性、乳化安定性、増粘性、結着性などの機能を発揮するようにァラ ビアガムを改質することが求められている。 [0004] In addition, the price of gum arabic rises sharply during the poor season because the production amount of gum arabic fluctuates greatly due to natural factors such as the climate and the conditions of the production area. For this reason, it is necessary to perform a function so as to exhibit functions such as emulsifying property, emulsifying stability, thickening property, and binding property in as little amount as possible. There is a need to modify beer gum.
[0005] 例えば、天然のアラビアガムのバラツキに由来する乳化性の不均衡さを少なくし、ま た乳化力を高めるための方法として、(1)アラビアガム力も金属イオンを除いてァラビ ン酸を取得し、これを加温変性する方法 (例えば、特許文献 1参照) ; (2)乾燥減量が 5 0重量%以下のアラビアガムを 60〜140°Cで 30分以上加温して変性する方法 (例え ば、特許文献 2参照) ; (3)相対湿度が 30〜: LOO%の雰囲気下で 40°C以上に加温し てアラビアガムを改質する方法 (例えば、特許文献 3参照) ;及び (4)乾燥減量 3%以下 の条件下で加熱してアラビアガムを改質する方法 (例えば、特許文献 4参照)などが提 案されている。  [0005] For example, as a method for reducing the imbalance in emulsifiability due to variations in natural gum arabic and increasing emulsifying power, (1) arabic acid can also be used to remove arabic acid from metal ions. (2) A method of denaturing gum arabic with a loss on drying of 50% by weight or less at 60 to 140 ° C for 30 minutes or longer. (See, for example, Patent Document 2); (3) A method of modifying gum arabic by heating to 40 ° C or higher in an atmosphere of relative humidity 30 to LOO% (see, for example, Patent Document 3); And (4) A method of modifying gum arabic by heating under the condition of loss on drying of 3% or less (for example, see Patent Document 4).
[0006] し力しながら、(1)の方法では期待されるほどの高い乳化性を有するアラビアガムは 得られず、アラビアガムを改質する方法としては十分でない。(2)〜(4)の方法は、確か に品質のバラツキを少なくして、乳化力も向上することができるが、十分な乳化効果 を持たせるためには高温で長時間の加熱を必要とするため、処理条件によっては着 色や焦げた臭い (着香)が発生する場合があり、使用する用途によっては風味や外 観を損なう可能性がある。  However, with the method (1), gum arabic having high emulsifiability as expected cannot be obtained, and it is not sufficient as a method for modifying gum arabic. The methods (2) to (4) can certainly reduce the quality variation and improve the emulsifying power, but in order to have a sufficient emulsifying effect, heating at a high temperature for a long time is required. Therefore, depending on the processing conditions, coloring and burnt odor (flavoring) may occur, and depending on the application used, the flavor and appearance may be impaired.
[0007] ところで、放射線照射技術は、ポリビニルアルコール (PVA)、ポリエチレンォキサイ ド (PEO)、及びポリビニルピロリドン (PVP)等の高分子物質を改質する目的で、広く 使用されている。また、カルボキシメチルセルロース (CMC)やその誘導体である CM デンプンゃ CM キトサン、またはセルロース誘導体であるメチルセルロースゃヒド ロキシプロピルセルロースでは、水を添カ卩し、良く練ってペースト状にしたものに電離 放射線を照射すると重合が起こり、ゲル強度が向上したり、ハイド口ゲルとなり吸水性 が向上することが知られている(例えば、特許文献 5、 6)。  [0007] By the way, radiation irradiation technology is widely used for the purpose of modifying polymer substances such as polyvinyl alcohol (PVA), polyethylene oxide (PEO), and polyvinylpyrrolidone (PVP). Carboxymethylcellulose (CMC) and its derivatives, CM starch, CM chitosan, and cellulose derivatives, methylcellulose, hydroxypropylcellulose, are charged with ionizing radiation when added to water and kneaded into a paste. It is known that when irradiated, polymerization occurs and gel strength is improved, or it becomes a hydrated gel and water absorption is improved (for example, Patent Documents 5 and 6).
[0008] し力しながら、上記記載の高分子物質以外の多糖類については、一般的に放射線 を照射すると、糖類の主鎖が切断され、分解反応が進み、分子量の低下が見られ、 乳化性、粘性及び結着性などの物性が低下することが知られて!/、る (非特許文献 3参 照)。 [0008] However, with regard to polysaccharides other than the above-described polymeric substances, generally, when irradiated with radiation, the main chain of the saccharide is cleaved, the decomposition reaction proceeds, the molecular weight decreases, and emulsification occurs. It is known that physical properties such as property, viscosity, and binding properties are reduced! /, (See Non-Patent Document 3).
[0009] アラビアガムもこの報告と違わず、アラビアガムの玉状物、粉砕品、スプレードライ粉 末に放射線照射しても、上記の高分子物質とは異なって重合反応は見られず、逆に わずかに粘性が低下することが知られている (非特許文献 4参照)。このように、従来、 アラビアガムに放射線照射することによって機能を向上させることができるとの予見は なかった。 [0009] Gum arabic is no different from this report, and when irradiated with gum arabic balls, crushed products, and spray-dried powders, unlike the polymer materials described above, the polymerization reaction is not observed. In It is known that the viscosity slightly decreases (see Non-Patent Document 4). Thus, there has been no prediction that the function can be improved by irradiating gum arabic with radiation.
非特許文献 1: iNDUSTRIAL GUMS - Polysaccharides and Their Derivatives―」 , SE COND EDITION, ACADEMIC PRESS, New York and London, 1973, pp.197— 263 非特許文献 2 :Williams,P.A. and Phillips,G.O.,(2000) in Handbook of Hydrocolloids, Editors Williams, P.A. and Phillips, G.O. pp.155— 168,Woodhead, London and New York  Non-patent document 1: iNDUSTRIAL GUMS-Polysaccharides and Their Derivatives- ", SE COND EDITION, ACADEMIC PRESS, New York and London, 1973, pp.197-263 Non-patent document 2: Williams, PA and Phillips, GO, (2000) in Handbook of Hydrocolloids, Editors Williams, PA and Phillips, GO pp.155—168, Woodhead, London and New York
非特許文献 3 :「The effects of radiation on carbohydrates」 Phillips, CO., Chapter26 P.1217— 1297, The Carbohydrates Second edition.  Non-Patent Document 3: "The effects of radiation on carbohydrates" Phillips, CO., Chapter 26 P.1217— 1297, The Carbohydrates Second edition.
非特許文献 4:「The effect of sterilizing doses of y -irradiation on the molecular wei ght and emulsification properties of gum ArabicJ Blake, et al, Food Hydrocolloids 1 Non-Patent Document 4: “The effect of sterilizing doses of y-irradiation on the molecular wei ght and emulsification properties of gum ArabicJ Blake, et al, Food Hydrocolloids 1
988, Vol2 No.5 P.407-415 988, Vol2 No.5 P.407-415
特許文献 1:特開平 02— 049001号公報  Patent Document 1: Japanese Patent Laid-Open No. 02-049001
特許文献 2 :特開 2000— 166489号公報  Patent Document 2: JP 2000-166489 A
特許文献 3 :特願 2002— 156166号  Patent Document 3: Japanese Patent Application No. 2002-156166
特許文献 4:特願 2003— 318958号  Patent Document 4: Japanese Patent Application No. 2003-318958
特許文献 5 :特開 2004— 45543号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-45543
特許文献 6:特開 2003— 160602号公報  Patent Document 6: Japanese Unexamined Patent Publication No. 2003-160602
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0010] 本発明は、高い乳化力を備えるように改質してなるアラビアガムを製造するための 新規な方法を提供することを目的とする。さらに本発明は、こうして得られた乳化力に 優れたアラビアガム、並びに該アラビアガムの乳化剤としての用途を提供することを 目的とする。 [0010] An object of the present invention is to provide a novel method for producing gum arabic that is modified to have high emulsifying power. Furthermore, an object of the present invention is to provide gum arabic excellent in emulsifying power obtained in this way and use of the gum arabic as an emulsifier.
課題を解決するための手段  Means for solving the problem
[0011] 本発明者らは、上記課題のもと鋭意研究を重ねていたところ、アラビアガムの水溶 物に γ線や電子線などの電離放射線を照射することにより、水溶物中のアラビアガム の分子量が増加し、アラビアガムの乳化力が向上することを見いだした。 [0011] The inventors of the present invention have made extensive studies based on the above-mentioned problems. As a result, the gum arabic in the aqueous solution is irradiated with ionizing radiation such as γ rays and electron beams. It has been found that the molecular weight of the gum increases and the emulsifying power of gum arabic improves.
[0012] 本発明は力かる知見に基づいて開発されたものであり、下記の態様を含むものであ る:  [0012] The present invention has been developed on the basis of strong knowledge and includes the following aspects:
項 1.アラビアガム水溶物に電離放射線を照射する工程を有する改質アラビアガムの 製造方法。  Item 1. A method for producing modified gum arabic, comprising a step of irradiating an aqueous gum arabic solution with ionizing radiation.
項 2.アラビアガム水溶物のアラビアガムの濃度が 15〜60重量0 /0であることを特徴と する項 1記載の改質アラビアガムの製造方法。 Section 2. production method of the modified gum arabic of claim 1, wherein the concentration of gum arabic gum arabic aqueous material is from 15 to 60 weight 0/0.
項 3.電離放射線が γ線であることを特徴とする項 1に記載する改質アラビアガムの 製造方法。  Item 3. The process for producing a modified gum arabic according to Item 1, wherein the ionizing radiation is gamma rays.
項 4.電離放射線が加速電圧 0. 2〜: LOMeVの電子線であることを特徴とする項 1〖こ 記載する改質アラビアガムの製造方法。  Item 4. The method for producing modified gum arabic according to Item 1, wherein the ionizing radiation is an electron beam having an acceleration voltage of 0.2 to: LOMeV.
項 5.電離放射線の吸収線量が l〜50kGyであることを特徴とする項 1に記載する改 質アラビアガムの製造方法。  Item 5. The method for producing modified gum arabic according to Item 1, wherein the absorbed dose of ionizing radiation is 1 to 50 kGy.
項 6.アラビアガム濃度 15〜50重量0 /0のアラビアガム水溶物に 10〜50kGyの吸収 線量の電離放射線を照射するか、またはアラビアガム濃度 50〜60重量%のアラビア ガム水溶物に 3〜 30kGyの吸収線量の電離放射線を照射する工程を有する、項 1 記載の改質アラビアガムの製造方法。 Item 6. 3 Arabic gum concentration 15 to 50 weight 0/0 to gum arabic water was irradiating ionizing radiation absorbed dose 10~50kGy or arabic gum concentration 50-60% by weight of gum arabic water of Item 2. The method for producing modified gum arabic according to Item 1, comprising a step of irradiating ionizing radiation with an absorbed dose of 30 kGy.
項 7.アラビアガム水溶物に電離放射線を照射する工程の後に、乾燥工程を有する 項 1に記載する改質アラビアガムの製造方法。  Item 7. The method for producing modified gum arabic according to Item 1, wherein the method comprises a drying step after the step of irradiating the gum arabic aqueous solution with ionizing radiation.
項 8.乾燥工程が、スプレードライまたはドラムドライであることを特徴とする項 7記載 の改質アラビアガムの製造方法。  Item 8. The process for producing a modified gum arabic according to Item 7, wherein the drying step is spray drying or drum drying.
[0013] 項 9.項 1乃至 7のいずれかに記載する製造方法によって得られる改質アラビアガ ム。 [0013] Item 9. A modified Arabicum obtained by the production method according to any one of Items 1 to 7.
項 10.項 9に記載する改質アラビアガムを有効成分とする乳化剤。  Item 10. An emulsifier comprising the modified gum arabic described in Item 9 as an active ingredient.
[0014] 項 11.項 9に記載する改質アラビアガムを乳化剤として用いる乳化組成物の調製 方法。 [0014] Item 11. A method for preparing an emulsified composition using the modified gum arabic described in Item 9 as an emulsifier.
項 12.乳化組成物力 oZw型エマルシヨンまたは wZoZw型エマルシヨンである 項 11記載の乳化組成物の調製方法。 項 13.項 9に記載する改質アラビアガムを乳化剤として用いて、精油、油性香料、油 性色素、油溶性ビタミン、多価不飽和脂肪酸、動植物油、ショ糖酢酸イソ酪酸エステ ル、及び中鎖トリグリセライドからなる群力 選択される少なくとも 1種の疎水性物質を 親水性溶媒に分散安定化する工程を有する項 11記載の乳化組成物の調製方法。 Item 12. Emulsion composition strength The method for preparing an emulsion composition according to Item 11, which is oZw type emulsion or wZoZw type emulsion. Item 13. Using modified gum arabic as described in Item 9 as an emulsifier, essential oil, oily fragrance, oily pigment, oil-soluble vitamin, polyunsaturated fatty acid, animal and vegetable oil, sucrose acetate isobutyrate ester, and medium Item 12. The method for preparing an emulsified composition according to Item 11, comprising a step of dispersing and stabilizing at least one selected hydrophobic substance in a hydrophilic solvent.
[0015] 項 14.項 9に記載する改質アラビアガムを乳化剤として用いて調製される乳化組成 物。 [0015] An emulsified composition prepared using the modified gum arabic described in Item 14. as an emulsifier.
項 15.項 11に記載される調製方法で得られる項 14記載の乳化組成物。  Item 15. The emulsified composition according to Item 14, obtained by the preparation method according to Item 11.
項 16.飲食品である項 14記載の乳化組成物。  Item 16. The emulsified composition according to Item 14, which is a food or drink.
発明の効果  The invention's effect
[0016] 本発明の方法によれば、原料として用いる天然 (未改質)のアラビアガムの水溶物 を電離放射線で照射処理することにより、乳化力、特に乳化安定性に優れた改質ァ ラビアガムを取得することができる。特に本発明は、上記処理方法を採用することによ つて、従来公知の加熱による改質方法で問題となって 、た処理時の着色や付着によ る塊化を防止しながらも、効率よく良好な乳化力を有するアラビアガムを取得すること ができる有用な方法である。  [0016] According to the method of the present invention, a modified Arabica gum excellent in emulsifying power, particularly emulsification stability, is obtained by irradiating a natural (unmodified) gum arabic aqueous solution used as a raw material with ionizing radiation. Can be obtained. In particular, the present invention adopts the above-mentioned treatment method, which is a problem in the conventionally known reforming method by heating, and efficiently prevents the agglomeration due to coloring or adhesion during the treatment. This is a useful method by which gum arabic having good emulsifying power can be obtained.
[0017] 斯くして調製される本発明の改質アラビアガムは、精油、油性色素、油性香料、油 溶性ビタミン等の各種の疎水性物質の乳化に好適に使用することができる。本発明 の改質アラビアガムを用いて調製されるエマルシヨン (乳化組成物)は、通常使用され る天然アラビアガムを用いて調製したエマルシヨンと比較して、粒子の粒度分布が均 一であり、かつ、加熱、長期保存または経時変化などの虐待により、エマルシヨン粒 子同士が、凝集したり、合一して粒子が劣化することが有意に抑制されており、非常 に安定である。  [0017] The modified gum arabic of the present invention thus prepared can be suitably used for emulsification of various hydrophobic substances such as essential oils, oil-based pigments, oil-based fragrances, and oil-soluble vitamins. The emulsion (emulsion composition) prepared using the modified gum arabic of the present invention has a uniform particle size distribution compared to the emulsion prepared using natural gum arabic commonly used, and It is extremely stable because the emulsion particles are agglomerated or coalesced due to abuse such as heating, long-term storage, or aging, and the particles are deteriorated by coalescence.
図面の簡単な説明  Brief Description of Drawings
[0018] [図 1]試料 1 (アラビアガムパウダー)、試料 2〜5 (20、 35、 50及び 60重量%のァラビ ァガム水溶物)に対して電子線照射を行った際の、分子量の変化を示した図である。  [0018] [Fig. 1] Changes in molecular weight of sample 1 (gum arabic powder) and samples 2 to 5 (20, 35, 50, and 60% by weight aqueous gum arabic gum) when irradiated with an electron beam FIG.
[図 2]試料 1 (アラビアガムパウダー)、試料 2〜5 (20、 35、 50及び 60重量%のァラビ ァガム水溶物)に対して電子線照射を行った際の、粘度変化を示した図である。  [Figure 2] Diagram showing changes in viscosity when sample 1 (gum arabic powder) and samples 2 to 5 (20, 35, 50 and 60% by weight aqueous gum arabic gum) were irradiated with an electron beam It is.
[図 3]試料 1 (アラビアガムパウダー)、試料 2〜5 (20、 35、 50及び 60重量0 /0のァラビ ァガム水溶物)に対して電子線照射を行った際の、着色度の変化を示した図である。 発明を実施するための最良の形態 [3] Sample 1 (gum arabic powder), Arabi sample 2-5 (20, 35, 50 and 60 weight 0/0 It is the figure which showed the change of the coloring degree at the time of performing an electron beam irradiation with respect to an agam aqueous solution. BEST MODE FOR CARRYING OUT THE INVENTION
[0019] (1)改質アラビアガムの製造方法  [1] Method for producing modified gum arabic
本発明は、アラビアガムを高い乳化力を有するように改質する方法、言い換えれば 高い乳化力を有するように改質してなるアラビアガムの製造方法である。本発明の方 法は、アラビアガム水溶物に電離放射線を照射することによって実施することができ る。なお、本願発明でいう「乳化力」には、乳化処理時の乳化力とその経時的安定性 の両方の特性が含まれる。また本明細書にぉ 、て「乳化性」と!、う場合は前者の特性 、「乳化安定性」と!、う場合は後者の特性を意味する。  The present invention is a method for modifying gum arabic to have high emulsifying power, in other words, a method for producing gum arabic obtained by modifying gum arabic to have high emulsifying power. The method of the present invention can be carried out by irradiating an aqueous gum arabic solution with ionizing radiation. The “emulsifying power” as used in the present invention includes both the emulsifying power during the emulsification treatment and its stability over time. In the present specification, “emulsification” means the former characteristic, and “emulsification stability” means “the latter characteristic”.
[0020] 本発明の方法において、改質対象物(出発原料)として用いられるアラビアガムは、 マメ科植物であるアカシア属に属するアカシア ·セネガル (Acacia Senegal)やァカシ ァ ·セィアル (Acacia seval)またはこれらの同属植物の幹や枝力 得られる天然滲出 物である。または、これをさらに精製処理、脱塩処理または粉砕もしくはドライスプレ 一などの加工処理を施したものであってもよ 、。  [0020] In the method of the present invention, gum arabic used as a modification target (starting material) is Acacia Senegal or Acacia seval belonging to the genus Acacia which is a leguminous plant. It is a natural exudate obtained from the trunk and branch strength of these genus plants. Alternatively, it may be subjected to further purification treatment, desalting treatment, or processing such as pulverization or dry spraying.
これらの原料は、本発明の改質アラビアガムと区別する意味で、本発明において単 に「アラビアガム」 t 、うか、または「天然アラビアガム」若しくは「未改質アラビアガム」 と称する。  In the present invention, these raw materials are simply referred to as “gum arabic” t, or “natural gum arabic” or “unmodified gum arabic” in the sense of being distinguished from the modified gum arabic of the present invention.
[0021] 天然アラビアガム (A.senegal種)は、通常、エチオピア力もセネガルにかけての北ァ フリカや西アフリカの各国(エチオピア、スーダン、セネガノレ、ナイジェリア、 -ジエー ル、ガーナ)、ケニアやウガンダなど東アフリカの国々、アフリカのサハラ地帯、並びに ナイル川支流の盆地地帯でも産出されるが、本発明においてはその由来を問うこと なぐいずれの産地由来のものであってもよい。  [0021] Natural gum arabic (A. senegal species) is usually found in North Africa and Ethiopian powers in Senegal and countries in West Africa (Ethiopia, Sudan, Seneganore, Nigeria, -Gier, Ghana), Kenya, Uganda and other East African countries In the Saharan region of Africa, the basin region of the Nile tributary, but in the present invention, it may be derived from any production region without questioning its origin.
[0022] 通常天然のアラビアガムは、塊状物、玉状物、粗粉砕物、顆粒状、粒状、または粉 末状 (スプレードライ粉末を含む)の形態で入手することができる。本発明ではこれら の形状を問わず、 V、ずれの形態のものをも改質対象のアラビアガムとして使用するこ とがでさる。  [0022] Normally, natural gum arabic can be obtained in the form of a lump, ball, coarsely pulverized product, granule, granule, or powder (including spray-dried powder). In the present invention, regardless of these shapes, V and misalignment can be used as the gum arabic to be modified.
[0023] 電離放射線を照射するアラビアガム水溶物は、これらのさまざまな形態の天然のァ ラビアガム (未改質アラビアガム)を水に溶解することによって調製される。ここで使用 される水は、特に制限されず、水道水、蒸留水、イオン交換水のいずれであってもよ い。好ましくはイオン交換水である。 [0023] Aqueous gum arabic solution to be irradiated with ionizing radiation is prepared by dissolving these various forms of natural Arabica gum (unmodified gum arabic) in water. Used here Water to be used is not particularly limited, and may be tap water, distilled water, or ion exchange water. Ion exchange water is preferable.
[0024] アラビアガム水溶物のアラビアガム濃度は、使用するアラビアガムの種類やその分 子量によっても異なる力 通常 15〜60重量%の範囲力も選択することができる。好ま しくは 30〜55重量0 /0、より好ましくは 35〜50重量%である。アラビアガム水溶物の アラビアガムの濃度が 15重量%よりも力なり低くなると、電離放射線を照射しても改 質が十分に進まなくなる傾向があり、効率的に改質することが難しくなる。一方、ァラ ビアガム濃度が 60重量%を越えてかなり高くなると、アラビアガムを水中に均一 '均 質に溶解することが難しくなるため、水溶物中に濃度のムラができ、一定した品質の ものが得られなくなる傾向がある。 The concentration of gum arabic in the aqueous gum arabic solution varies depending on the type of gum arabic used and the amount of the gum arabic, and a force in the range of usually 15 to 60% by weight can also be selected. 30-55 is properly preferred weight 0/0, more preferably 35 to 50 wt%. If the concentration of gum arabic in the gum arabic aqueous solution is lower than 15% by weight, the modification tends not to proceed sufficiently even when irradiated with ionizing radiation, making it difficult to improve efficiently. On the other hand, when the gum arabia gum concentration exceeds 60% by weight, it becomes difficult to evenly dissolve gum arabic in water evenly. Tends to be lost.
[0025] なお、アラビアガム水溶物は、アラビアガムを必要に応じて加温した水に溶解した 後、不溶物や混入して 、るゴミなどを遠心分離またはフィルタープレス濾過により取り 除 、ておくことが好ま 、 (固液分離)。  [0025] It should be noted that the gum arabic aqueous solution is prepared by dissolving gum arabic in water that has been heated as necessary, and then removing insoluble matter and mixed waste by centrifugation or filter press filtration. It is preferred (solid-liquid separation).
[0026] 電離放射線の照射は、このようにして調製されたアラビアガム水溶物を、照射する 電離放射線の種類に応じて、任意の容器にいれた状態で行うことができる。但し、ぺ 一スト状などアラビアガム水溶物の流動性が低い場合は、容器に収容することなぐ 直に電離放射線を照射することも可能である。  [0026] Irradiation with ionizing radiation can be performed in a state where the aqueous gum arabic solution thus prepared is placed in an arbitrary container depending on the type of ionizing radiation to be irradiated. However, if the gum arabic aqueous solution has a low fluidity, such as a paste, it is possible to irradiate it with ionizing radiation immediately without placing it in a container.
[0027] 電離放射線の種類としては、特に制限されず電離放射線( y線、電子線、 X線)の いずれをも使用することができる。好ましくは γ線または電子線である。  [0027] The type of ionizing radiation is not particularly limited, and any of ionizing radiation (y-ray, electron beam, X-ray) can be used. Gamma rays or electron beams are preferred.
[0028] γ線は電子線と比較して透過力が大きいので、厚みのある試料を照射する場合に 適した線源である。また γ線が透過する限りにおいて、試料の収納に使用する容器 の種類が制限されないという利点がある。例えば、 γ線によれば大型のドラム缶ゃス テンレス容器に大量の試料を入れて照射することも可能であり、これによりアラビアガ ム水溶物を一度に大量に照射処理 (改質処理)することができる。  [0028] Since γ-rays have a larger transmission power than electron beams, they are suitable for irradiating a thick sample. Moreover, as long as γ-rays are transmitted, there is an advantage that the type of container used for storing the sample is not limited. For example, with γ-rays, it is possible to irradiate a large amount of sample in a large drum can stainless steel container, so that a large amount of Arabic aqueous solution can be irradiated (modified) at once. it can.
[0029] γ線照射には、放射性同位元素としてセシウム 137を使用した照射とコノ レト 60を 使用した照射があるが、好ましくはコバルト 60を使用した γ線照射である。コバルト 6 0の場合は、ステンレス製のカプセル中に密閉した状態で使用すれば、環境汚染な どの問題がなく安全かつ容易に取り扱うことができるのに対して、セシウム 137はコバ ルト 60と比較して、安全な取り扱いが容易でないことや単位時間当たりの線量、すな わち線量率が低く照射効率が悪!、と 、う短所がある。 [0029] The γ-ray irradiation includes irradiation using cesium 137 as a radioisotope and irradiation using conoret 60, and γ-ray irradiation using cobalt 60 is preferable. In the case of cobalt 60, when used in a sealed capsule made of stainless steel, it can be handled safely and easily without problems such as environmental pollution. Compared to the default 60, it has the disadvantages that it is not easy to handle safely and the dose per unit time, that is, the dose rate is low and the irradiation efficiency is poor!
[0030] 一方、電子線は、 γ線のようにコバルト 60やセシウム 137のような放射性同位元素 を使用しないため、遮蔽装置も比較的簡易な物でも良いなど、安全面や作業面で好 ましい線源である。また電子線照射は、単位時間当たりの線量、すなわち線量率が 高ぐ処理能力が大きいといわれている。  [0030] On the other hand, electron beams do not use radioisotopes such as cobalt 60 and cesium 137 like γ-rays, so shielding devices may be relatively simple, which is preferable in terms of safety and work. A source of radiation. In addition, electron beam irradiation is said to have a high treatment capacity due to a high dose per unit time, that is, a dose rate.
[0031] 電子線は加速電圧に応じて透過力が異なるものの、一般に γ線に比して透過力が 小さい。このため、使用する電子線の透過力(電子線のエネルギー)に応じて照射試 料 (アラビアガム水溶物)を調整することが好ましい。例えば、 lOMeV程度の高エネ ルギ一の電子線を用いる場合は、照射試料の厚さを数 mn!〜 3cm程度など比較的 厚く調整した場合でも均一に照射することが可能である。一方、 IMeV以下の低エネ ルギ一の電子線を用いる場合は、均一に照射するためには、試料の厚さを 3mm以 下に調整することが好まし 、。  [0031] Although the transmission power of electron beams varies depending on the acceleration voltage, the transmission power is generally smaller than that of gamma rays. For this reason, it is preferable to adjust the irradiation sample (gum arabic gum aqueous solution) according to the transmission power (electron beam energy) of the electron beam used. For example, when using a high energy electron beam of about lOMeV, the thickness of the irradiated sample should be several mn! Even when the thickness is adjusted to be relatively thick, such as about 3 cm, uniform irradiation is possible. On the other hand, when using a low-energy electron beam of IMeV or less, it is preferable to adjust the sample thickness to 3 mm or less in order to irradiate uniformly.
[0032] このように、電子線照射は、照射する試料が厚みのな!、ものや厚みを調整すること が可能なもの (例えば、粉体、流体、液体、薄層化可能な固体)であれば、前述する ように処理能力が大きく大量処理が可能であるため、経済的にも工業的製造の観点 からも、より好ましい照射法である。  [0032] As described above, the electron beam irradiation is performed with a sample to be irradiated having a small thickness, or a sample whose thickness can be adjusted (for example, powder, fluid, liquid, thinnable solid). If so, it is a more preferable irradiation method from the viewpoint of economical and industrial production because it has a large processing capacity and can be processed in large quantities as described above.
[0033] なお、電子線照射は、電子加速器を利用して行うことが好ま 、。加速電圧として、 特に制限されないが、通常 0.2〜: LOMeV程度、好ましくは通常 0.3〜8MeV程度を 挙げることができる。  [0033] It is preferable that the electron beam irradiation is performed using an electron accelerator. The acceleration voltage is not particularly limited, but is usually about 0.2 to about LOMeV, preferably about 0.3 to 8 MeV.
[0034] 照射電離放射線として電子線を使用する場合は、通常、試料をポリエチレン袋に充 填し、電子線のエネルギーに応じてその厚みを調整することが行われる。具体的に は、照射試料 (アラビアガム水溶物)をポリエチレン袋に充填し、できるだけ均一にな るように薄く広げて照射する方法を挙げることができる。特に、上記の IMeV以下の 低エネルギーの電子線を用いる場合は、できるだけ薄いポリエチレン袋に厚さが 3m m以下になるように試料を入れ、薄くシート状にして照射することが好ましい。このよう に電子線を使用する場合は照射試料の厚みが制限されるので、効率的に多数の試 料を処理するためには照射試料を薄く広げてコンベア上で移動させながら電子線を 照射することが好ましい。また片面力 だけでなく両面力 照射する方法も好適に利 用される。 [0034] When an electron beam is used as the irradiating ionizing radiation, a sample is usually filled in a polyethylene bag and the thickness thereof is adjusted according to the energy of the electron beam. Specifically, the irradiation sample (gum arabic gum aqueous solution) is filled in a polyethylene bag, and spreads thinly and irradiates it as uniformly as possible. In particular, when using a low energy electron beam of IMeV or less, it is preferable to irradiate the sample in a thin sheet with a sample placed in a polyethylene bag that is as thin as possible. When an electron beam is used in this way, the thickness of the irradiated sample is limited, so in order to efficiently process a large number of samples, the irradiated sample is spread thinly and moved on the conveyor. Irradiation is preferred. In addition to the single-sided force, a method of irradiating the double-sided force is also preferably used.
[0035] なお、これらの照射条件は、照射するアラビアガム水溶物の流動性やその比重、ま たはこれを収容する包材 (容器)など、さまざまな要因に適した条件を選択使用するこ とがでさる。  [0035] It should be noted that these irradiation conditions are selected and used according to various factors such as the fluidity and specific gravity of the gum arabic aqueous solution to be irradiated, or the packaging material (container) that accommodates it. Togashi.
[0036] 照射試料としてアラビアガム濃度が 15〜50重量%の流動性のあるアラビアガム水 溶物を用いる場合、特に制限はされないが、改質アラビアガムの製造効率の点から、 コバルト 60を用いた γ線や lOMeV程度の高エネルギーの電子線など、比較的透過 力の高い電離放射線を使用するほうが好ましい。好適な照射方法として、コバルト 60 を用いて γ線を照射する場合、密閉可能なドラム缶やアトロン缶やステンレス容器に アラビアガム水溶物を入れて照射する方法を例示することができる。また、高工ネル ギ一の電子線を照射する場合、アルミニウムやポリエチレン製の容器にアラビアガム 水溶液を入れて密閉し、厚さを数 mn!〜 3cm程度またはそれ以下に調整して照射す る方法を挙げることがでさる。  [0036] When a gum arabic solution having fluidity of 15 to 50% by weight of gum arabic is used as an irradiation sample, there is no particular limitation, but from the viewpoint of production efficiency of modified gum arabic, cobalt 60 is used. It is preferable to use ionizing radiation with relatively high transmission power, such as gamma rays and high-energy electron beams of about lOMeV. As a suitable irradiation method, when γ-rays are irradiated using cobalt 60, a method of irradiating a gum arabic gum aqueous solution in a sealable drum can, an Atron can, or a stainless steel container can be exemplified. Also, when irradiating high-energy energy, the gum arabic aqueous solution is sealed in an aluminum or polyethylene container and the thickness is several mn! The method of adjusting the irradiation to about 3 cm or less can be mentioned.
[0037] 一方、照射試料としてアラビアガム濃度が 50〜60重量%の、流動性が少ないァラ ビアガム水溶物(ペースト)を用いる場合も、改質アラビアガムの製造効率の点から、 上記と同様にコバルト 60を用いた γ線や lOMeV程度の高エネルギーの電子線など 、比較的透過力の高い電離放射線を使用するほうが好ましい。その際、電子線照射 を行う場合は、コンベアの上にポリエチレン製のシートを敷いておき、その上部に、口 一ラーなどで適切な厚さ(好ましくは数 mn!〜 3cm程度またはそれ以下)に調整した ペースト状のアラビアガム水溶物を薄く広げて照射する方法を例示することができる。 これにより連続的にかつ大量にアラビアガム水溶物に電子線を照射することが可能と なる。また、ポリエチレン製の袋にペースト状のアラビアガム水溶物を入れて、上記の ように厚さを調整して照射することも可能である。  [0037] On the other hand, in the case of using an aqueous gum arabic gum solution (paste) with low fluidity and a gum arabic concentration of 50 to 60% by weight as the irradiated sample, the same as above from the viewpoint of the production efficiency of the modified gum arabic It is preferable to use ionizing radiation with relatively high transmission power, such as gamma rays using cobalt 60 and high-energy electron beams of about lOMeV. At that time, when electron beam irradiation is performed, a polyethylene sheet is laid on the conveyor, and an appropriate thickness (preferably about several mn! To 3 cm or less) is used on the top of the sheet. The paste-like gum arabic aqueous solution adjusted to 1 can be spread and irradiated. This makes it possible to irradiate the gum arabic aqueous solution with an electron beam continuously and in large quantities. It is also possible to put a paste-like gum arabic aqueous solution in a polyethylene bag and adjust the thickness as described above for irradiation.
[0038] アラビアガム水溶物に照射する電離放射線の吸収線量は本発明の効果が得られる 限り特に制限されない。アラビアガム水溶物中のアラビアガムの濃度によって好適な 吸収線量は異なるが、通常 l〜50kGyの範囲力も適宜選択して利用できる。例えば アラビアガムの濃度が 15〜50重量%のアラビアガム水溶物の場合は、電離放射線 照射による重合速度がやや遅い傾向がある。このため、吸収線量は 10〜50kGyの 範囲が好ましぐより好ましくは 20〜40kGyの範囲である。一方、アラビアガムの濃度 が 50〜60重量%のアラビアガム水溶物の場合は、電離放射線照射による重合速度 が速い傾向にある。このため、好ましい吸収線量の範囲は 3〜30kGyであり、より好 ましくは 10〜25kGyの範囲である。なお、電離放射線の吸収線量は、定法に従って 測定することができる。具体的には、例えばフリッケ線量計で校正した CTA線量計( 例えば、 FTR-125, Fuji Photo Film Co. Ltdなど)を用いて測定する方法を例示する ことができる。 [0038] The absorbed dose of ionizing radiation applied to the gum arabic aqueous solution is not particularly limited as long as the effect of the present invention is obtained. Although a suitable absorbed dose varies depending on the concentration of gum arabic in the gum arabic aqueous solution, a range power of usually 1 to 50 kGy can be appropriately selected and used. For example, in the case of gum arabic aqueous solution with a gum arabic concentration of 15-50% by weight, ionizing radiation The polymerization rate due to irradiation tends to be slightly slow. For this reason, the absorbed dose is preferably in the range of 10-50 kGy, more preferably in the range of 20-40 kGy. On the other hand, in the case of gum arabic aqueous solution having a gum arabic concentration of 50-60% by weight, the polymerization rate by ionizing radiation tends to be high. For this reason, the preferred absorbed dose range is 3-30 kGy, more preferably 10-25 kGy. The absorbed dose of ionizing radiation can be measured according to a standard method. Specifically, for example, a measurement method using a CTA dosimeter (for example, FTR-125, Fuji Photo Film Co. Ltd, etc.) calibrated with a Fricke dosimeter can be exemplified.
[0039] 電離放射線で照射したアラビアガム水溶物は、そのままの状態または適当に水に 希釈した後に、スプレードライ、ドラムドライ、凍結乾燥などの慣用の方法で乾燥する ことができ、固体状態の改質アラビアガムとして提供することもできる。上記の乾燥方 法のほか、工業的な乾燥方法として、減圧乾燥機や真空乾燥機等の乾燥装置を利 用して乾燥する方法を用いることもできる。これらの装置では、水流ポンプや真空ポ ンプなどでアラビアガム水溶物を収容した容器内の圧力を低下させるとともにその内 容物(アラビアガム水溶物)をスクリューなどにより均一に混合することができる。し力も 、当該装置には、容器の外部のジャケットに蒸気を導入することによって当該内容物 を加熱することができる装置も付設できるため、乾燥 (水分除去)、混合、および加熱と いう操作を一度に行うことができる。さらに、当該装置によれば、加熱終了後は、容器 の外部のジャケットに冷却水を通水しながら内容物を混合することにより、内容物を 速やかに冷却することもできる。これらの具体的な装置の例としては、リボコーン (円錐 型リボン真空乾燥機 (RM— VD型):株式会社大川原製作所製)、真空型ナウタミキ サ NXV型 (ホソカワミクロン株式会社製)、遊星運動型円錐型混合乾燥機 SVミキサー (神鋼パンテック株式会社製)などを挙げることができる。乾燥処理によって調製される 改質アラビアガムの形態は、特に制限されないが、粉末状、粒状、顆粒状を例示する ことができる。  [0039] The gum arabic aqueous solution irradiated with ionizing radiation can be dried as it is or appropriately diluted with water and then dried by a conventional method such as spray drying, drum drying, freeze drying, etc. It can also be provided as quality gum arabic. In addition to the drying method described above, a drying method using a drying apparatus such as a vacuum dryer or a vacuum dryer can also be used as an industrial drying method. In these devices, the pressure in the container containing the gum arabic aqueous solution can be lowered by a water pump or a vacuum pump, and the content (gum arabic gum aqueous solution) can be uniformly mixed with a screw or the like. However, since the apparatus can be equipped with an apparatus that can heat the contents by introducing steam into the jacket outside the container, operations such as drying (moisture removal), mixing, and heating are performed once. Can be done. Further, according to the apparatus, after the heating is completed, the contents can be rapidly cooled by mixing the contents while passing cooling water through the jacket outside the container. Examples of these specific devices are: Ribocon (conical ribbon vacuum dryer (RM-VD type): manufactured by Okawara Seisakusho Co., Ltd.), vacuum type Nautamixa NXV type (manufactured by Hosokawa Micron Co., Ltd.), planetary motion type cone Examples include a type mixing dryer SV mixer (manufactured by Shinko Pantech Co., Ltd.). The form of the modified gum arabic prepared by the drying treatment is not particularly limited, and examples thereof include powder, granules and granules.
[0040] 上記の本発明の製造方法によれば、原料として用いた天然 (未改質)アラビアガム に比して高い乳化力、特に高い乳化安定性を発揮するように改質されてなるアラビア ガムを製造取得することができる。斯くして得られる改質アラビアガムのうち、乳化力( 特に乳化安定性)性の観点から好ましいものとしては、重量平均分子量が 100万以 上のちのを挙げることがでさる。 [0040] According to the production method of the present invention described above, an Arabidopsis modified so as to exhibit high emulsifying power, particularly high emulsification stability, compared with natural (unmodified) gum arabic used as a raw material. Gum can be manufactured and acquired. Among the modified gum arabic thus obtained, emulsifying power ( Particularly preferred from the viewpoint of emulsion stability) are those having a weight average molecular weight of 1 million or more.
[0041] さらに本発明の方法によれば、従来の加熱方法で問題となっている着色、着香また はケーキングなどといった、取り扱い上または添加剤として他製品に適用するにあた つて支障になる不都合を低減した状態で、乳化力が改善向上されたアラビアガムを 製造取得することができる。よって、本発明は、アラビアガムを、着色化を低減した状 態で乳化力、特に乳化安定性を高めるように改質する方法ともいうことができる。  [0041] Further, according to the method of the present invention, it is difficult to apply to other products as an additive or as an additive such as coloring, flavoring or caking, which is a problem in the conventional heating method. With reduced inconvenience, gum arabic with improved emulsifying power can be produced and obtained. Therefore, the present invention can also be referred to as a method of modifying gum arabic so as to increase emulsifying power, particularly emulsification stability, in a state where coloring is reduced.
[0042] このため、本発明の製造方法によって得られる改質アラビアガムは、乳化剤として、 食品、香粧品、医薬品若しくは医薬部外品など、特に色や臭いが品質に与える影響 の大きい製品に好適に使用することができる。本発明の改質アラビアガムの製造方 法は、前述する電離放射線の照射工程、または電離放射線の照射工程及び乾燥ェ 程に加えて、さらに、改質アラビアガムを乳化剤として各種製品 (食品、香粧品、医薬 品若しくは医薬部外品など)に適用するために必要な処理工程を備えて 、てもよ!/、。 また、乳化剤として好適な状態 (組成や形態)に調製するための処理工程を備えてい てもよい。  [0042] Therefore, the modified gum arabic obtained by the production method of the present invention is suitable as an emulsifier for foods, cosmetics, pharmaceuticals or quasi-drugs, particularly products having a great influence on the quality of color and odor. Can be used for In addition to the ionizing radiation irradiation process or ionizing radiation irradiation process and the drying process described above, the method for producing the modified gum arabic of the present invention further includes various products (food, aroma, etc.) using the modified gum arabic as an emulsifier. It may be provided with processing steps necessary for application to cosmetics, pharmaceuticals or quasi-drugs! In addition, a treatment step for preparing a suitable state (composition or form) as an emulsifier may be provided.
[0043] (2)乳化剤及び乳化組成物の調製方法  [0043] (2) Preparation method of emulsifier and emulsified composition
上記の方法によって調製される改質アラビアガムは、高 、乳化力にお 、て原料とし て用いた未改質アラビアガム (天然アラビアガム)と明確に区別することができる。一 般に乳化剤の乳化力は、調製されるエマルシヨンの平均粒子径が小さいほど、また その粒子径が経時的に安定して保持されるほど、優れていると評価される(「アラビア ゴムで乳化した OZWェマルジヨンの濁度比法による研究」、薬学雑誌、 112(12)、 90 6— 913、(1992) )。なお、ここで改質アラビアガムの乳化力の評価に用いるェマル シヨン (乳化組成物)の調製方法、その平均粒子径の測定方法及び乳化の経時的安 定性 (乳化安定性)の評価方法については、後述する実験例に記載する方法に従う ことができる。  The modified gum arabic prepared by the above method can be clearly distinguished from unmodified gum arabic (natural gum arabic) used as a raw material with high emulsifying power. In general, the emulsifying power of an emulsifier is evaluated to be superior as the average particle size of the prepared emulsion is smaller and the particle size is more stably maintained over time (“Emulsification with Arabic gum”). OZW Emulsion by turbidity ratio method ", Pharmaceutical Journal, 112 (12), 90 6-913, (1992)). Here, regarding the preparation method of emulsion (emulsion composition) used for the evaluation of the emulsifying power of the modified gum arabic, the measurement method of the average particle diameter, and the evaluation method of stability over time (emulsification stability) The method described in the experimental examples described later can be followed.
[0044] 本発明の改質アラビアガムは、乳化剤として、特に食品、医薬品、医薬部外品、ま たは香粧品の分野において、とりわけ経口的に摂取され得る製品の乳化剤として好 適に使用することができる。具体的には、飲料、粉末飲料、デザート、チューイングガ ム、錠菓、スナック菓子、水産加工品、畜産加工品、レトルト食品などの食品等の乳 ィ匕、油性香料の乳化、油性色素の乳化などに、乳化剤として好適に使用することが できる。上記改質アラビアガムは電離放射線照射後そのままの水溶物の状態で、ま たは乾燥処理後の固体状態 (例えば粒子状若しくは粉末状)で乳化剤として用いるこ ともできるが、必要に応じて、これらにその他の担体や添加剤を配合して乳化剤とし て調製することもできる。この場合、使用される担体や添加剤は、乳化剤を用いる製 品 (例えば、食品、医薬品、医薬部外品、または香粧品)の種類やその用途に応じて[0044] The modified gum arabic of the present invention is suitably used as an emulsifier, particularly as an emulsifier for products that can be taken orally, particularly in the field of food, pharmaceuticals, quasi drugs, or cosmetics. be able to. Specifically, beverages, powdered beverages, desserts, chewing gum It can be suitably used as an emulsifier for dairy products such as foodstuffs, tablet confectionery, snack confectionery, processed fishery products, processed livestock products, and retort foods, emulsified oily fragrances, and emulsified oily pigments. The modified gum arabic can be used as an emulsifier in the state of an aqueous solution as it is after irradiation with ionizing radiation or in the solid state after drying (for example, in the form of particles or powder). In addition, other carriers and additives can be blended to prepare an emulsifier. In this case, the carrier or additive used depends on the type of product using the emulsifier (for example, food, medicine, quasi-drug, or cosmetic) and its use.
、常法に従って適宜選択採用することができる。例えば、デキストリン、マルトース、乳 糖等の糖類やグリセリン、プロピレングリコール等の多価アルコールと混合して使用 することができる。なお、担体や添加剤を配合して乳化剤を調製する場合、当該乳化 剤中に含まれる改質アラビアガムの割合としては、制限されないが、少なくとも下限はThese can be appropriately selected and employed in accordance with conventional methods. For example, it can be used by mixing with saccharides such as dextrin, maltose and lactose and polyhydric alcohols such as glycerin and propylene glycol. When preparing an emulsifier by blending carriers and additives, the proportion of the modified gum arabic contained in the emulsifier is not limited, but at least the lower limit is
5重量%以上、好ましくは 10重量%以上であることが望ましい。なお、上限は 100重 量%未満であれば特に制限されな!、。 It is desirable that the content be 5% by weight or more, preferably 10% by weight or more. The upper limit is not particularly limited as long as it is less than 100% by weight! ,.
[0045] また、本発明は上記改質アラビアガムを乳化剤として使用するエマルシヨン (乳化組 成物)の調製方法を提供する。当該エマルシヨンは、上記改質アラビアガムを乳化剤 として使用して、疎水性物質 (分散質)を親水性溶媒 (分散媒)中に分散安定化する ことによって調製することができる。ここでエマルシヨン (乳化組成物)としては、水中 油滴(oZw)型や wZoZw型のエマルシヨンを挙げることができる。 [0045] The present invention also provides a method for preparing an emulsion (emulsified composition) using the modified gum arabic as an emulsifier. The emulsion can be prepared by dispersing and stabilizing a hydrophobic substance (dispersoid) in a hydrophilic solvent (dispersion medium) using the modified gum arabic as an emulsifier. Examples of emulsion (emulsified composition) include oil-in-water (oZw) type and wZoZw type emulsion.
[0046] ここで乳化される疎水性物質は、通常エマルシヨン形態に供されるもの若しくはその 必要性のあるものであれば特に制限されないが、好ましくは食品、医薬品、医薬部外 品または香粧品分野で用いられるもの、より好ましくは経口的に用いられることが可 能な可食性疎水性物質を挙げることができる。  [0046] The hydrophobic substance to be emulsified here is not particularly limited as long as it is ordinarily provided in emulsion form, but is preferably in the food, pharmaceutical, quasi-drug or cosmetic field. And edible hydrophobic substances that can be used orally.
[0047] 具体的には、オレンジ、ライム、レモン及びグレープフルーツなどの柑橘系植物等 の基原植物から得られる各種精油、ペッパー、シンナモン及びジンジャーなどの基原 植物力 ォレオレジン方式で得られるォレオレジン、ジャスミンやローズなどの基原植 物からアブソリユート方式で得られるアブソリユート、その他、合成香料化合物、及び 油性調合香料組成物などの油性香料; j8 -カロチン、パプリカ色素、リコピン、パーム 油カロチン、ドナリエラカロチン及びニンジンカロチンなどの油性色素;ビタミン A, D, E及び Kなどの脂溶性ビタミン;ドコサへキサェン酸、エイコサペンタエン酸、及び Ύ リノレン酸などの多価不飽和脂肪酸;大豆油、菜種油、コーン油及び魚油などの動 植物油脂; SAIB (Sucrose Acetate isobutyrate:ショ糖酢酸イソ酪酸エステル)、また は C6〜C12の中鎖トリグリセライドなどの加工食品用油脂及びこれら可食性油性材 料の任意の混合物を例示することができる。 [0047] Specifically, various essential oils obtained from basic plants such as citrus plants such as orange, lime, lemon and grapefruit, and basic plant powers such as pepper, cinnamon and ginger. Oleoresin and jasmine obtained by oleoresin method Oils, such as absolute, obtained from the basic plant such as rose and rose, etc., other synthetic fragrance compounds, and oil-based compound fragrance compositions; j8-carotene, paprika pigment, lycopene, palm oil carotene, donariella carotene and carrot Oily pigments such as carotene; vitamins A, D, Fat-soluble vitamins such as E and K; Polyunsaturated fatty acids such as docosahexaenoic acid, eicosapentaenoic acid, and Ύlinolenic acid; Animal and vegetable oils such as soybean oil, rapeseed oil, corn oil and fish oil; SAIB (Sucrose Acetate isobutyrate : Sucrose acetate isobutyrate) or processed food oils such as C6-C12 medium chain triglycerides and any mixture of these edible oily materials.
[0048] 上記改質アラビアガムを用いたエマルシヨンの調製方法は、特に制限されず、水中 油滴(OZW)型エマルシヨンまたは WZOZW型エマルシヨンの調製に関する常法 に従って、疎水性物質と親水性溶媒とを上記改質アラビアガムの存在下で、ホモジ ナイザーや高圧噴射などを利用して機械的に攪拌乳化することによって行うことがで きる。より具体的には、下記の方法を例示することができる。  [0048] The method of preparing the emulsion using the modified gum arabic is not particularly limited, and the hydrophobic substance and the hydrophilic solvent are added according to a conventional method for preparing oil-in-water (OZW) type emulsion or WZOZW type emulsion. In the presence of the modified gum arabic, it can be carried out by mechanically stirring and emulsifying using a homogenizer, high-pressure jet or the like. More specifically, the following method can be illustrated.
[0049] まず、改質アラビアガムを水等の親水性溶媒に溶解し、必要に応じて、遠心分離又 はフィルタープレス等を利用した濾過など、適当な固液分離手段により不純物を除去 して、改質アラビアガム水溶液を調製する。これに、分散質として用いる目的の疎水 性物質 (例えば油脂、また予め油脂に香料や色素を溶解した混合液)を撹拌機等で 混合し、予備乳化する。なお、この際、必要に応じて SAIB等の比重調整剤にて比重 を調整してもよい。次いで得られた予備乳化混合液を、乳化機を利用して乳化する。  [0049] First, the modified gum arabic is dissolved in a hydrophilic solvent such as water, and if necessary, impurities are removed by an appropriate solid-liquid separation means such as centrifugation or filtration using a filter press. A modified gum arabic aqueous solution is prepared. To this, a desired hydrophobic substance used as a dispersoid (for example, oil and fat, or a mixed solution in which a fragrance or a pigment is previously dissolved in oil or fat) is mixed with a stirrer and pre-emulsified. At this time, the specific gravity may be adjusted with a specific gravity adjusting agent such as SAIB as necessary. Next, the obtained pre-emulsified mixture is emulsified using an emulsifier.
[0050] なお、ここで疎水性物質として油性香料や油性色素を用いて乳化香料や乳化色素 を調製する場合は、上記疎水性物質として予め油脂に油性香料や油性色素を溶解 した混合液を用いることが好ましい。これによつて、より乳化を安定ィ匕し、また成分の 揮発を予防することができる。また油性香料や油性色素を溶解する油脂としては、特 に制限されないが、通常、中鎖トリグリセライド (炭素数 6〜12の脂肪酸トリダリセライド )、及びコーン油、サフラワー油、または大豆油などの植物油を用いることができる。  [0050] Here, when an emulsified fragrance or an emulsified dye is prepared using an oily fragrance or an oily dye as the hydrophobic substance, a mixed solution in which the oily fragrance or the oily dye is previously dissolved in an oil or fat is used as the hydrophobic substance. It is preferable. As a result, the emulsification can be further stabilized and the volatilization of the components can be prevented. Oils and fats that dissolve oily fragrances and oily pigments are not particularly limited, but usually, medium chain triglycerides (triglycerides having 6 to 12 carbon atoms) and vegetable oils such as corn oil, safflower oil, or soybean oil are used. Can be used.
[0051] 乳化に使用する乳化機としても、特に制限はなぐ目的とするエマルシヨンの粒子の 大きさや、試料の粘度などに応じて適宜選択することができる。例えば、機械的に高 圧のホモジナイザーの他、ナノマイザーゃデイスパーミル、コロイドミルなどの乳化機 を使用することができる。  [0051] The emulsifier used for emulsification can be appropriately selected according to the size of the target emulsion particles, the viscosity of the sample, and the like, which are not particularly limited. For example, in addition to a mechanically high pressure homogenizer, an emulsifier such as a nanomizer or disperser mill or colloid mill can be used.
[0052] 乳化工程は、前述するように、親水性溶媒中に、攪拌下で、疎水性物質を添加し、 攪拌して予備乳化し、粒子径約 2〜5 μ m程度の乳化粒子を調製した後、ホモジナイ ザ一やナノマイザ一などの乳化機を用いて微細で均一な粒子 (例えば、平均粒子径[0052] In the emulsification step, as described above, a hydrophobic substance is added to a hydrophilic solvent under stirring, and the mixture is stirred and pre-emulsified to prepare emulsified particles having a particle size of about 2 to 5 μm. And then homogenize Fine and uniform particles (e.g., average particle size) using an emulsifier such as
1 μ m以下、好ましくは 0.8 μ m以下)を調製することによって行うことができる。なお、 β一力ロチンなどの色素の多くは、それ自身、結晶の状態でサスペンションとして存 在する。したがって、これらの色素をエマルシヨン (乳化色素)として調製するには、ま ず色素の結晶を適当な油脂と高温下で混合し溶解してから、親水性溶媒に添加する ことが好ましい。 1 μm or less, preferably 0.8 μm or less). Many pigments such as β-strength rotins themselves exist as suspensions in the crystalline state. Therefore, in order to prepare these dyes as emulsions (emulsified dyes), it is preferable that the dye crystals are first mixed with an appropriate oil and fat at high temperature and dissolved, and then added to a hydrophilic solvent.
[0053] エマルシヨンの調製に際して、使用される改質アラビアガムの割合は特に制限され ないが、エマルシヨン 100重量%中の割合として、通常 5〜20重量%を挙げることが できる。  [0053] In the preparation of emulsion, the ratio of the modified gum arabic used is not particularly limited, but the ratio in 100% by weight of emulsion usually includes 5 to 20% by weight.
[0054] 斯くして改質アラビアガムを用いて調製されるエマルシヨン (乳化組成物)は、通常 の天然アラビアガム〔未改質アラビアガム〕を用いて調製したエマルシヨンと比較して 、粒子の粒度分布が均一であり、また、加熱や長期保存などにより、エマルシヨン粒 子同士が、凝集したり、合一して粒子が劣化することが有意に抑制されており、高い 経時的安定性を備えて 、る。  [0054] Thus, the emulsion (emulsion composition) prepared using the modified gum arabic has a particle size smaller than that of the emulsion prepared using ordinary natural gum arabic [unmodified gum arabic]. The distribution is uniform, and the emulsion particles are agglomerated or coalesced by heating and long-term storage, etc., and the deterioration of the particles is significantly suppressed, providing high stability over time. RU
[0055] 改質アラビアガムを使用して調製したエマルシヨンを用いて作られる食品としては、 特に制限はされないが、例えば、乳飲料、乳酸菌飲料、炭酸飲料、果実飲料、粉末 飲料、スポーツ飲料、紅茶飲料、緑茶飲料などの飲料類;カスタードプリン、ミルクプリ ンなどのプリン類;ゼリー、ババロア及びヨーグルトなどのデザート類;ミルクアイスタリ ーム、アイスキャンディーなどの冷菓類;チューインガムや風船ガムのガム類;マーブ ルチョコレートなどのコーティングチョコレートの他、メロンチョコレートなどの香味を付 与したチョコレートなどのチョコレート類;ノヽードキャンディー、ソフトキャンディー、キヤ ラメル、ドロップなどのキャラメル類;ノヽードビスケット、クッキー、おかきなどの焼き菓 子類;コーンスープ、ポタージュスープなどのスープ類、ドレッシング、ケチャップ、マ ヨネーズ、たれ、ソースなどのソース類;ノヽム、ソーセージ、焼き豚などの蓄肉加工品; 魚肉ソーセージ、蒲鋅などの水産練り製品;バター、マーガリン、チーズなどの油脂 製品類などの加工食品を例示することができる。  [0055] The food made using the emulsion prepared using the modified gum arabic is not particularly limited. For example, milk drink, lactic acid bacteria drink, carbonated drink, fruit drink, powder drink, sports drink, tea Beverages such as beverages and green tea beverages; puddings such as custard pudding and milk pudding; desserts such as jelly, bavaroa and yogurt; frozen confectionery such as milk ice cream and ice candy; chewing gum and bubble gum gum; Coated chocolate such as marble chocolate, chocolate such as melon chocolate, etc .; caramels such as node candy, soft candy, caramel, and drop; node biscuits, cookies, and okaki Baked goods such as corn soup Sauces such as pork and potage soup, dressings, ketchup, mayonnaise, sauce, sauces and other sauces; processed meat products such as sausages, sausages and grilled pork; fish paste products such as fish sausages and salmon; butter, margarine, Fats and oils such as cheese Examples of processed foods such as products.
実施例  Example
[0056] 以下、試験例及び実施例を挙げて本発明を説明するが、本発明はこれらの実施例 などに限定されるものではない。なお、以下の実験例において、吸収線量はフリッケ 線量計で校正した CTA線量計 (FTR-125, Fuji Photo Film Co. Ltd)を用いて測定し た。Hereinafter, the present invention will be described with reference to test examples and examples. However, the present invention is not limited to these examples. It is not limited to such as. In the following experimental examples, the absorbed dose was measured using a CTA dosimeter (FTR-125, Fuji Photo Film Co. Ltd) calibrated with a Fricke dosimeter.
Figure imgf000017_0001
Figure imgf000017_0001
(1)被験試料の調製  (1) Preparation of test sample
(1-1) スプレードライされた粉末状のアラビアガム〔 S§M 、 MW60万、乾燥減量 7. 0%] (試料 1)を厚さ 0. 04mmのポリエチレン袋(ュ-パック G— 8、生産日本株式 会社製:横 140mm X縦 200mm)に試料の厚さ約 3mmになるように 50gを入れ、均 一な状態とし、ファンデグラフ電子加速装置を用いて加速電圧 0. 8MeV、線量率 60 OkGyZhrの条件で、 10、 20、 30、及び 50kGyのそれぞれの吸収線量で電子線を 照射した (電子線照射試料 1)。  (1-1) Spray-dried powdered gum arabic [S§M, MW 600,000, loss on drying 7.0%] (Sample 1) in a 0.04 mm thick polyethylene bag (New Pack G-8, Produced by Nippon Stock Co., Ltd. (140 mm wide x 200 mm long), put 50 g so that the thickness of the sample is about 3 mm, make it uniform, and use a vandegraph electron accelerator to accelerate voltage 0.8 MeV, dose rate 60 Electron beams were irradiated with absorbed doses of 10, 20, 30, and 50 kGy under the conditions of OkGyZhr (electron beam irradiation sample 1).
[0058] (1-2) スプレードライされた粉末状のアラビアガム (A.Smigsal、 MW60万、乾燥減 量 7. 0%)をイオン交換水に配合して、アラビアガムの濃度が 20重量0 /0 (試料 2)、 35 重量% (試料 3)、 50重量% (試料 4)、 60重量% (試料 5)となるように、アラビアガム 水溶物を調製した。これらの水溶物を各々厚さ 0. 04mmのポリエチレン袋(ュ -パッ ク G— 8、生産日本株式会社製:横 140mm X縦 200mm)に厚さが約 3mmになるよ うに試料水溶物を 75g入れ、ファンデグラフ電子加速装置を用いて加速電圧 0. 8M eV、線量率 600kGyZhrの条件で、各試料(試料 2〜5)に対して 10、 20、 30、及び 50kGyの吸収線量で電子線を各々照射した (電子線照射試料 2〜5)。 [0058] (1-2) a spray-dried powdered gum arabic (A.Smigsal, MW60 ten thousand, dried down weight 7.0%) was blended in ion-exchanged water, the concentration of gum arabic 20 weight 0 An aqueous solution of gum arabic was prepared so as to be / 0 (sample 2), 35 wt% (sample 3), 50 wt% (sample 4), and 60 wt% (sample 5). 75 g of the sample water solution is placed in a polyethylene bag with a thickness of 0.04 mm (manufactured by Nippon Co., Ltd .: 140 mm wide x 200 mm long) so that the thickness is about 3 mm. Then, using a van der graph electron accelerator, an electron beam is absorbed with an absorbed dose of 10, 20, 30, and 50 kGy for each sample (samples 2 to 5) under the conditions of an acceleration voltage of 0.8 MeV and a dose rate of 600 kGyZhr. Each was irradiated (electron beam irradiated samples 2 to 5).
[0059] (2)物性評価  [0059] (2) Physical property evaluation
上記で調製した電子線照射試料 1〜5について、下記に記載する方法に従って、 (i )重量平均分子量、(ii)着色度、及び (iii)粘度を評価した。  For the electron beam irradiated samples 1 to 5 prepared above, (i) the weight average molecular weight, (ii) the degree of coloring, and (iii) the viscosity were evaluated according to the methods described below.
[0060] (i)重量平均分子量  [0060] (i) Weight average molecular weight
アラビアガムの重量平均分子量は、光散舌 L (MALLS :Multi Angle Laser Light Sea ttering)検出器、屈折率 (RI)検出器及び UV検出器の 3つの検出器をオンラインで 接続したゲル濾過クロマトグラフィー(GPC— MALLS)の手法によって測定し、得ら れたデータを ASTRA Version 4.5(Wyatt Technology)ソフトウェアにて処理することに より求めることができる。なお、当該 GPC— MALLS手法によれば、光散乱(MALL S)検出器により分子量を、屈折率 (RI)検出器により各成分の重量 (組成比)を、さら に UV検出器により蛋白質を検出することができ、分子量既知の標準品と対比するこ となく分析成分の分子量並びに組成を求めることができる。その詳細な原理や特徴 は Idris,O.H.M.,Williams,P.A.,Phillips, G.O. ; Food Hydrocolloids, 12,375-388(1998) J に記載されている。 The weight average molecular weight of gum arabic is measured by gel filtration chromatography with three detectors connected online, a light scattering tongue (MALLS) detector, a refractive index (RI) detector, and a UV detector. (GPC-MALLS) can be obtained by measuring with the ASTRA Version 4.5 (Wyatt Technology) software. According to the GPC-MALLS method, light scattering (MALL S) The molecular weight can be detected by the detector, the weight (composition ratio) of each component can be detected by the refractive index (RI) detector, and the protein can be detected by the UV detector. The molecular weight and composition of the analytical component can be determined without any problem. Its detailed principles and features are described in Idris, OHM, Williams, PA, Phillips, GO; Food Hydrocolloids, 12,375-388 (1998) J.
[0061] 本発明で採用した GPC— MALLSの測定条件は下記の通りである:  [0061] The measurement conditions of GPC-MALLS employed in the present invention are as follows:
カフム : buperose 6 10/300 uL、 mersham Biosciences, Sweden;  Kahum: buperose 6 10/300 uL, mersham Biosciences, Sweden;
流速 :0.5ml/分  Flow rate: 0.5ml / min
溶出溶媒 :0.2M NaCl  Elution solvent: 0.2M NaCl
試料の調製:分析試料 (電子線照射試料)を溶出溶媒 (0. 2M NaCl)にて希釈した 後、 0. 45 mセルロースアセテートメンブランフィルタにて不溶物を除去した液を測 定する。  Sample preparation: After the analysis sample (electron beam irradiated sample) is diluted with the elution solvent (0.2 M NaCl), measure the solution from which insolubles have been removed with a 0.45 m cellulose acetate membrane filter.
試料濃度 :0.1% (WZV)  Sample concentration: 0.1% (WZV)
試料液注入量: 100 μ \  Sample solution injection volume: 100 μ \
dn/dc : 0.141  dn / dc: 0.141
温度 :室温  Temperature: Room temperature
検出器 : 1) MALLS (multi angle laser light scattering): DAWN EOS(Wyatt T echnology社製,米国)、 2) RI (屈折率)、 3) UV (214nmでの吸収)。  Detector: 1) MALLS (multi angle laser light scattering): DAWN EOS (Wyatt Technology, USA), 2) RI (refractive index), 3) UV (absorption at 214 nm).
[0062] 上記条件で、 RI検出器によって求められたクロマトグラム上のピーク全体 (チャート のベースラインからの RIチャートの立ち上がり部を起点及び降下してベースラインと 交わった部分を終点とした場合に、当該起点力も終点までの RIチャート部分を意味 する。)を 1ピークとしてデータ処理した場合 (processed as one peak)に、重量換算で 求めた分子量を「重量平均分子量」とした。乳化力の増加に伴い、「重量平均分子量 」も増加することから、乳化性を評価する一つの指標とすることができる。  [0062] Under the above conditions, the entire peak on the chromatogram obtained by the RI detector (when the rising edge of the RI chart from the baseline of the chart starts and descends and the intersection with the baseline is the end point) The starting force also means the RI chart part to the end point.) When the data was processed as one peak (processed as one peak), the molecular weight determined by weight conversion was defined as the “weight average molecular weight”. As the emulsifying power increases, the “weight average molecular weight” also increases, which can be used as an index for evaluating emulsifiability.
[0063] (ii)着色度  [0063] (ii) Degree of coloring
電子線照射試料 1については、試料 10gにイオン交換水 90gを添加し、よく混合し てアラビアガム 10重量%水溶物を調製した。電子線照射試料 2〜5は、イオン交換 水を用いてアラビアガムの濃度が 10重量%となるように調整した。 [0064] これらの溶液(10重量%濃度の水溶物として調整した各電子線照射試料)を光路 長 10mmの石英セルに入れ紫外可視分光光度計 V— 560(日本分光 (株)製)を用い て透過光にて測定し、ハンター表色系 (Lab表色系)の 3刺激値を求め、 (a2 + b2) を計算して着色度とした。 For sample 1 irradiated with electron beam, 90 g of ion-exchanged water was added to 10 g of the sample and mixed well to prepare a 10% by weight aqueous solution of gum arabic. Electron beam irradiated samples 2 to 5 were prepared using ion-exchanged water so that the gum arabic concentration was 10% by weight. [0064] These solutions (each sample irradiated with an electron beam adjusted as a 10% by weight aqueous solution) were placed in a quartz cell having an optical path length of 10 mm, and an ultraviolet-visible spectrophotometer V-560 (manufactured by JASCO Corporation) was used. Measured with transmitted light, the tristimulus value of the Hunter color system (Lab color system) was determined, and (a 2 + b 2 ) was calculated as the coloring degree.
[0065] (m)粘度  [0065] (m) Viscosity
電子線照射試料 1については、試料 lOgにイオン交換水 90gを添加し、よく混合し てアラビアガム 10重量%水溶物を調製した。電子線照射試料 2〜5は、イオン交換 水を用いてアラビアガムの濃度が 10重量%となるように調整した。  For electron beam irradiated sample 1, 90 g of ion exchange water was added to sample lOg and mixed well to prepare a 10% by weight aqueous solution of gum arabic. Electron beam irradiated samples 2 to 5 were prepared using ion-exchanged water so that the gum arabic concentration was 10% by weight.
[0066] 上記のように 10重量%濃度の水溶物として調整した各電子線照射試料を、各々 1 00ml容スクリュー管に入れ、 20°Cにて B型回転粘度計 (BM型、株式会社トキメック 製)にて、ローター No. 1、回転数 60rpmの条件で粘度 (mPa' s)を測定した (ロータ 一 No. 1で測定できない試料についてはローター No. 2にて、同様に回転数 60rpm の条件で粘度 (mPa · s)を測定した)。  [0066] Each electron beam irradiation sample prepared as a 10% by weight aqueous solution as described above was placed in a 100 ml screw tube, and a B-type viscometer (BM type, Tokimec Co., Ltd.) at 20 ° C. ), The viscosity (mPa's) was measured under the conditions of rotor No. 1 and rotation speed of 60 rpm. (For samples that cannot be measured with rotor No. 1, use rotor No. 2 with the same rotation speed of 60 rpm.) Viscosity (mPa · s) was measured under the conditions).
[0067] 以上の測定の結果を表 1に示す。また、各試料 (試料 1〜5)に各吸収線量 (0〜50 kGy)の電子線を照射した際の分子量、粘度、及び着色度の変化を、各々図 1、 2お よび 3に示す。  [0067] Table 1 shows the results of the above measurements. Figures 1, 2 and 3 show the changes in molecular weight, viscosity, and coloring degree when each sample (Samples 1-5) was irradiated with an electron beam of each absorbed dose (0-50 kGy).
[0068] [表 1] [0068] [Table 1]
電子線照射した試料の物性変化 Changes in physical properties of samples irradiated with electron beam
Figure imgf000020_0001
Figure imgf000020_0001
[0069] この結果力 粉末状態で照射した試料 1については、吸収線量が上がるにつれて 分子量と粘度が低下し、このことから電子線の照射によってアラビアガムが分解され ていることがわかる。 [0069] As a result, for sample 1 irradiated in the powder state, the molecular weight and viscosity decreased as the absorbed dose increased, indicating that gum arabic was decomposed by electron beam irradiation.
[0070] 一方、アラビアガムの 20重量%水溶物、 35重量%水溶物、 50重量%水溶物、及 び 60重量%水溶物については(電子照射試料 2 5)、いずれも電子線の照射により 分子量と粘度の増加が認められたことから、アラビアガムが分解せずに逆に重合が 生じていると考えられる。  [0070] On the other hand, 20% aqueous solution, 35% aqueous solution, 50% aqueous solution, and 60% aqueous solution of gum arabic (electron-irradiated sample 25) were all irradiated with an electron beam. Since increases in molecular weight and viscosity were observed, it is considered that gum arabic was not decomposed but polymerized.
[0071] 着色度については、粉末(固体)状のアラビアガムに電子線照射する場合に比較し て、 20重量%水溶物、 35重量%水溶物、 50重量%水溶物、及び 60重量%水溶物 (電子照射試料 2 5)に照射した場合は、有意に着色度は低ぐ着色化が抑制され ていることが認められ、特に 35重量%水溶物及び 50重量%水溶物において最も着 色化が抑制されていた。このことから、 30 55重量%の水溶物濃度範囲での照射が 、着色を抑制した改質アラビアガムの調製により有用であることがわ力つた。 [0072] 実験例 2 [0071] Regarding the degree of coloring, 20% by weight aqueous solution, 35% by weight aqueous solution, 50% by weight aqueous solution, and 60% by weight aqueous solution compared to the case where powdered (solid) gum arabic is irradiated with an electron beam. When an object (electron-irradiated sample 25) is irradiated, it is recognized that coloring is significantly low, and coloring is suppressed most particularly in 35 wt% aqueous solution and 50 wt% aqueous solution. Was suppressed. This proved that irradiation in a 3055 wt% aqueous solution concentration range is more useful for the preparation of modified gum arabic with suppressed coloration. [0072] Experimental Example 2
(1)被験試料の調製  (1) Preparation of test sample
アラビアガムの玉 (A.SeneeaL MW60万、乾燥減量 7. 0%) 35kgに対して、 90°Cに加熱したイオン交換水 65kgを添加、攪拌混合する。これを遠心分離機によ つて、不溶物を除去した後、この上清液として 35重量%のアラビアガム水溶物を得た 。これを 2L容のステンレス製容器に 1. 5kg入れ、コバルト 60を用いて γ線を、 2.5、 5、 10、 20、 30、 40、及び 50kGyの吸収線量で照射した (線量率 lkGyZhr)。  Add 65 kg of ion-exchanged water heated to 90 ° C to 35 kg of gum arabic (A. SeneeaL MW 600,000, loss on drying 7.0%), and mix by stirring. After removing the insoluble matter with a centrifuge, 35% by weight of an aqueous solution of gum arabic was obtained as the supernatant. 1.5 kg of this was put into a 2 L stainless steel container, and γ-rays were irradiated with cobalt 60 at an absorbed dose of 2.5, 5, 10, 20, 30, 40, and 50 kGy (dose rate lkGyZhr).
[0073] (2)物性評価 [0073] (2) Physical property evaluation
上記で得られた各試料について、実験例 1の方法に従って重量平均分子量、粘度 、及び着色度を調べた。結果を表 2に示す。  For each of the samples obtained above, the weight average molecular weight, viscosity, and coloring degree were examined according to the method of Experimental Example 1. The results are shown in Table 2.
[0074] [表 2] [0074] [Table 2]
r線照射したアラビアガム 3 5 %水溶物の物性変化  Changes in physical properties of 35% aqueous solution of gum arabic irradiated with r-rays
Figure imgf000021_0001
Figure imgf000021_0001
[0075] (3)乳化力評価  [0075] (3) Emulsifying power evaluation
上記で得られた各試料にっ 、て、下記の方法に従って乳化力を評価した。 <方法 >  Each sample obtained above was evaluated for emulsifying power according to the following method. <Method>
γ線照射した 35重量0 /0アラビアガム水溶物 500gにイオン交換水 300gを添カロ混 合し、この溶液を攪拌下、中鎖トリグリセライド (オクタン酸'デカン酸トリグリセライド)で ある 0. D. 0 (商品名、日清オイリオ株式会社製) 200gを添加混合し、ホモジナイザ 一 (APV GAULIN社製)にて乳化しエマルシヨンを調製する(圧力 44MPa (450kg /cm2)でのホモジナイズを 4回)。 Attachment Caro combined mixed ion exchange water 300g into γ-ray irradiation was 35 weight 0/0 arabic gum aqueous was 500 g, while stirring the solution, 0. D. is a medium-chain triglyceride (octanoic 'decanoic acid triglyceride) 0 (Trade name, manufactured by Nisshin Oillio Co., Ltd.) Add 200g, mix and emulsify with homogenizer (manufactured by APV GAULIN) to prepare emulsion (4 times homogenization at 44MPa (450kg / cm 2 )).
[0076] 得られたエマルシヨンにつ!、て、乳化直後および 60°C3日間保存後の平均粒子径 m)を、粒度分布測定装置 SALD— 1100 (レーザー回折式、島津製作所 (株)製 )を用いて測定する。なお、一般に乳化剤の乳化力は、調製されるエマルシヨンの平 均粒子径が小さいほど、またその粒子径が経時的に安定して保持されるほど、優れ てレ、ると評価される(「アラビアゴムで乳化した o/wエマルシヨンの濁度比法による 研究」、薬学雑誌、 112(12)906— 913,(1992))。また、乳化安定性を、乳化直後と 60°C 3曰保存後の平均粒子径の差で評価した。 [0076] For the obtained emulsion !, the average particle size m) immediately after emulsification and after storage at 60 ° C for 3 days was measured using a particle size distribution analyzer SALD-1100 (laser diffraction type, manufactured by Shimadzu Corporation). Use to measure. In general, the emulsifying power of an emulsifier is equal to the level of the emulsion to be prepared. It is estimated that the smaller the average particle size and the more stable the particle size over time, the better it will be (“Study by the turbidity ratio method of o / w emulsion emulsified with gum arabic”). "Pharmacological Journal, 112 (12) 906-913, (1992)). Emulsification stability was also evaluated by the difference in average particle size immediately after emulsification and after storage at 60 ° C for 3 mm.
[0077] 乳化力の評価結果を表 3に示す。なお、エマルシヨンの経時変化安定性 (乳化安定 性)は、上記乳化直後のエマルシヨンの平均粒子径 (a)と加速試験 (60°C3日間保存) 後のエマルシヨンの平均粒子径 (b)との差 (b— a)力も判断することができる。ェマル シヨンの平均粒子径の変化が少ないほど、経時変化安定性 (乳化安定性)に優れて レ、ることを意味する。  [0077] Table 3 shows the evaluation results of emulsifying power. The stability of emulsion over time (emulsification stability) is the difference between the average particle diameter (a) of emulsion just after emulsification and the average particle diameter (b) of emulsion after accelerated test (stored at 60 ° C for 3 days). (b— a) Force can also be judged. The smaller the change in the average particle size of the emulsion, the better the stability with time (emulsification stability).
[0078] [表 3]  [0078] [Table 3]
Figure imgf000022_0001
Figure imgf000022_0001
[0079] 上記結果力 わ力るように、 y線照射しな 、未改質のアラビアガム水溶物を用いて 調製したエマルシヨンは、加速試験 (60°C、 3日保存)に供することにより、エマルショ ン粒子力 S劣ィ匕して、平均粒子径カ 0. 65 111カら1. 85 μ πιへと、 1. 20 μ πιの平均 粒子径の変化が見られた。これに対して、 γ線照射したアラビアガム水溶物を用いて 調製したエマルシヨンは、加速試験 (60°C、 3日保存)での平均粒子径の変化が有意 に小さくなり、経時変化安定性 (乳化安定性)は向上していることがわ力 た。 [0079] As shown in the above results, the emulsion prepared using an unmodified gum arabic aqueous solution without y-irradiation was subjected to an accelerated test (stored at 60 ° C for 3 days). As the emulsion particle force decreased, the average particle size changed from 1.65 μπι to 1.85 μπι to 1.85 μπι. In contrast, emulsions prepared using gamma-irradiated gum arabic aqueous solution showed significantly smaller changes in average particle size in accelerated tests (60 ° C, stored for 3 days), and stability over time ( Emulsification stability was improved.
[0080] 特に、電離放射線で 20kGy以上照射したアラビアガム水溶物を用いて調製したェ マルシヨンでは、加速試験(60°C、 3日保存)による平均粒子径の変化はほとんど見 られず、非常に高い乳化安定性を示した。また、 50kGy照射したアラビアガム水溶物 中には、若干量のゲル生成を認めた。このため、乳化性に優れた好適な水溶性の改 質アラビアガムを得るための吸収線量としては 50kGy以下が好ましいと考えられた。 [0081] 上記の実験例のうち、 30kGyで γ線照射したアラビアガム水溶物を乾燥し、下記 実施例にお!、て改質アラビアガムとして使用した。 [0080] In particular, in emulsions prepared using gum arabic aqueous solution irradiated with ionizing radiation at 20 kGy or more, there was almost no change in the average particle size due to the accelerated test (stored at 60 ° C for 3 days). High emulsification stability was exhibited. A small amount of gel was observed in the aqueous gum arabic solution irradiated with 50 kGy. Therefore, the absorbed dose for obtaining a suitable water-soluble modified gum arabic with excellent emulsifiability was considered to be preferably 50 kGy or less. [0081] Among the above experimental examples, an aqueous gum arabic solution irradiated with γ rays at 30 kGy was dried and used as modified gum arabic in the following examples.
[0082] 実施例 1 |8—力ロチン乳化製剤 (乳化色素製剤) [0082] Example 1 | 8—Strength Rotin Emulsified Formulation (Emulsified Dye Formulation)
<処方 >  <Prescription>
—力ロチン 30%懸濁液 5 (重量%)  —Power Rotin 30% Suspension 5 (wt%)
中鎖トリグリセライド 10  Medium chain triglyceride 10
改質アラビアガム 17  Modified gum arabic 17
Zt 68  Zt 68
合 計 100 重量%  Total 100% by weight
[0083] 改質アラビアガム 170gを水 680gに溶解し、 20重量0 /0のアラビアガム水溶液を調 製した。これを乳ィ匕剤として用いて、これに、予め β一力ロチン 30%懸濁液 50gに中 鎖トリグリセライド (オクタン酸 ·デカン酸トリグリセライド、 O. D. 0 (商品名、 日清製油 株式会社製) ) 100gを配合して 150°Cにて加熱して溶解してぉ 、た混合液を添加し 、攪拌混合した。これをホモジナイザー (APV GAULIN社製)にて乳化し (圧力 4. 4M Pa (450kgZcm2)でのホモジナイズを 4回)、乳化色素製剤である j8—力ロチン乳 化製剤を調製した。 [0083] The modified gum arabic 170g was dissolved in water 680 g, it was manufactured by adjusting the aqueous gum arabic solution of 20 weight 0/0. This was used as a wrinkle preparation, and medium chain triglyceride (octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)) 100 g was mixed and heated at 150 ° C. to dissolve, and the mixed solution was added and mixed with stirring. This was emulsified with a homogenizer (APV GAULIN) (4 times homogenization at a pressure of 4.4 MPa (450 kgZcm 2 )) to prepare an emulsified pigment preparation, j8-power rotin emulsion preparation.
[0084] 例 2 オレンジ乳化香料 (乳化香料)  [0084] Example 2 Orange emulsified flavor (emulsified flavor)
<処方 >  <Prescription>
オレンジ香料 2 (重量0 /0) Orange flavoring 2 (weight 0/0)
中鎖トリグリセライド 13  Medium chain triglyceride 13
改質アラビアガム 17  Modified gum arabic 17
Zt 68  Zt 68
合 計 100 重量%  Total 100% by weight
[0085] 改質アラビアガム 170gを水 680gに溶解し、 20重量0 /0のアラビアガム水溶液を調 製した。これを乳化剤として、これに、予めオレンジ香料 20gと中鎖トリグリセライド (ォ クタン酸 ·デカン酸トリグリセライド、 O. D. 0 (商品名、 日清製油株式会社製)) 130g を室温下でよく混合して調製しておいた混合液を添加し、攪拌混合した。これをホモ ジナイザー(APV GAULIN社製)にて乳化し(圧力 4. 4MPa (450kg/cm2)でのホ モジナイズを 4回)、乳化香料であるオレンジ乳化香料を調製した。 [0085] The modified gum arabic 170g was dissolved in water 680 g, it was manufactured by adjusting the aqueous gum arabic solution of 20 weight 0/0. Using this as an emulsifier, it was prepared by mixing in advance 20 g of orange fragrance and 130 g of medium chain triglyceride (octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)) at room temperature. The previously mixed liquid was added and mixed with stirring. This is emulsified with a homogenizer (APV GAULIN) (with a pressure of 4.4 MPa (450 kg / cm 2 )). The orange emulsified fragrance was prepared as an emulsified fragrance.
実施例 3 DHA (ドコサへキサェン酸)乳化製剤  Example 3 DHA (docosahexaenoic acid) emulsion formulation
<処方 >  <Prescription>
DHA20%含有魚油 5 (重量%)  Fish oil containing 20% DHA 5 (wt%)
中鎖トリグリセライド 10  Medium chain triglyceride 10
改質アラビアガム 17  Modified gum arabic 17
Zt 68  Zt 68
合 計 100 重量%  Total 100% by weight
[0087] 改質アラビアガム 170gを水 680gに溶解し、 20重量0 /0のアラビアガム水溶液を調 製した。これを乳化剤として、これに、予め DHA20重量%含有魚油 50gと中鎖トリグ リセライド (オクタン酸 ·デカン酸トリグリセライド、 O. D. 0 (商品名、 日清製油株式会 社製)) lOOgとの混合物を 80°Cに加熱し、混合して調製しておいた混合液を添加し 、攪拌混合した。これをホモジナイザー (APV GAULIN社製)にて乳化し (圧力 4. 4M Pa (450kg/cm2)でのホモジナイズを 4回)、 DHA乳化製剤を調製した。 [0087] The modified gum arabic 170g was dissolved in water 680 g, it was manufactured by adjusting the aqueous gum arabic solution of 20 weight 0/0. Using this as an emulsifier, a mixture of 50 g of fish oil containing 20% by weight of DHA and medium chain triglyceride (octanoic acid / decanoic acid triglyceride, OD 0 (trade name, manufactured by Nisshin Oil Co., Ltd.)) lOOg was added in advance to 80 °. The mixture prepared by heating to C and mixing was added and mixed by stirring. This was emulsified with a homogenizer (manufactured by APV GAULIN) (homogenization at a pressure of 4.4 MPa (450 kg / cm 2 ) four times) to prepare a DHA emulsion preparation.
[0088] 実飾 14 レモン粉末香料  [0088] Decoration 14 Lemon powder flavor
<処方 >  <Prescription>
レモンオイル 20 (重量0 /0) Lemon oil 20 (weight 0/0)
改質アラビアガム 20  Modified gum arabic 20
デキストリン 60  Dextrin 60
2t 150  2t 150
合 計 250 重量%  Total 250% by weight
[0089] 改質アラビアガム 200gとデキストリン 600gを水 1500gに溶解し、アラビアガム水溶 液を調製する。これを乳化剤として、これにレモンオイル 200gを添加し、攪拌混合す る。これをホモジナイザー(APV GAULIN社製)にて乳化する(圧力 2. 0MPa (200k g/cm2)でのホモジナイズを 1回)。次いで、この溶液をスプレードライヤー(ANHYD RO社製)(インレット 140。C、アウトレット 80。C)にて噴霧乾燥し、レモン粉末香料 95 Ogを調製する。 [0089] 200 g of modified gum arabic and 600 g of dextrin are dissolved in 1500 g of water to prepare an aqueous gum arabic solution. Using this as an emulsifier, add 200 g of lemon oil and stir and mix. This is emulsified with a homogenizer (APV GAULIN) (one homogenization at a pressure of 2.0 MPa (200 kg / cm 2 )). Next, this solution is spray-dried with a spray dryer (manufactured by ANHYD RO) (inlet 140.C, outlet 80.C) to prepare a lemon powder flavor 95 Og.

Claims

請求の範囲  The scope of the claims
[I] アラビアガム水溶物に電離放射線を照射する工程を有する改質アラビアガムの製 造方法。  [I] A method for producing modified gum arabic, comprising a step of irradiating an aqueous gum arabic solution with ionizing radiation.
[2] アラビアガム水溶物のアラビアガムの濃度が 15〜60重量%であることを特徴とする 請求項 1記載の改質アラビアガムの製造方法。  [2] The method for producing modified gum arabic according to claim 1, wherein the concentration of gum arabic in the gum arabic aqueous solution is 15 to 60% by weight.
[3] 電離放射線が γ線であることを特徴とする請求項 1に記載する改質アラビアガムの 製造方法。 [3] The method for producing a modified gum arabic according to claim 1, wherein the ionizing radiation is γ rays.
[4] 電離放射線が加速電圧 0. 2〜: LOMeVの電子線であることを特徴とする請求項 1 に記載する改質アラビアガムの製造方法。  [4] The method for producing modified gum arabic according to claim 1, wherein the ionizing radiation is an electron beam having an acceleration voltage of 0.2 to: LOMeV.
[5] 電離放射線の吸収線量が l〜50kGyであることを特徴とする請求項 1に記載する 改質アラビアガムの製造方法。 [5] The method for producing modified gum arabic according to claim 1, wherein the absorbed dose of ionizing radiation is 1 to 50 kGy.
[6] アラビアガム濃度 15〜50重量0 /0のアラビアガム水溶物に 10〜50kGyの吸収線量 の電離放射線を照射するか、またはアラビアガム濃度 50〜60重量%のアラビアガム 水溶物に 3〜30kGyの吸収線量の電離放射線を照射する工程を有する、請求項 1 記載の改質アラビアガムの製造方法。 [6] 3 in gum arabic concentration 15 to 50 weight 0/0 to gum arabic water was irradiating ionizing radiation absorbed dose 10~50kGy or arabic gum concentration 50-60% by weight of gum arabic water of The method for producing modified gum arabic according to claim 1, comprising a step of irradiating ionizing radiation with an absorbed dose of 30 kGy.
[7] アラビアガム水溶物に電離放射線を照射する工程の後に、乾燥工程を有する請求 項 1に記載する改質アラビアガムの製造方法。 7. The method for producing a modified gum arabic according to claim 1, further comprising a drying step after the step of irradiating the gum arabic aqueous solution with ionizing radiation.
[8] 乾燥工程が、スプレードライまたはドラムドライであることを特徴とする請求項 7記載 の改質アラビアガムの製造方法。 8. The method for producing a modified gum arabic according to claim 7, wherein the drying step is spray drying or drum drying.
[9] 請求項 1乃至 7の 、ずれかに記載する製造方法によって得られる改質アラビアガム [9] Modified gum arabic obtained by the production method according to any one of claims 1 to 7.
[10] 請求項 9に記載する改質アラビアガムを有効成分とする乳化剤。 [10] An emulsifier comprising the modified gum arabic according to claim 9 as an active ingredient.
[II] 請求項 9に記載する改質アラビアガムを乳化剤として用いる乳化組成物の調製方 法。  [II] A method for preparing an emulsified composition using the modified gum arabic described in claim 9 as an emulsifier.
[12] 乳化組成物力 OZW型エマルシヨンまたは WZOZW型エマルシヨンである請求 項 11記載の乳化組成物の調製方法。  [12] The method for preparing an emulsified composition according to claim 11, wherein the emulsified composition is OZW type emulsion or WZOZW type emulsion.
[13] 請求項 9に記載する改質アラビアガムを乳化剤として用いて、精油、油性香料、油 性色素、油溶性ビタミン、多価不飽和脂肪酸、動植物油、ショ糖酢酸イソ酪酸エステ ル、及び中鎖トリグリセライドからなる群力 選択される少なくとも 1種の疎水性物質を 親水性溶媒に分散安定化する工程を有する請求項 11記載の乳化組成物の調製方 法。 [13] Essential oil, oily fragrance, oily pigment, oil-soluble vitamin, polyunsaturated fatty acid, animal and vegetable oil, sucrose acetate isobutyric acid ester, using the modified gum arabic according to claim 9 as an emulsifier 12. The method for preparing an emulsified composition according to claim 11, further comprising a step of dispersing and stabilizing at least one hydrophobic substance selected from the group force consisting of water and medium chain triglyceride in a hydrophilic solvent.
[14] 請求項 9に記載する改質アラビアガムを乳化剤として用いて調製される乳化組成物  [14] An emulsified composition prepared using the modified gum arabic according to claim 9 as an emulsifier
[15] 請求項 11に記載される調製方法で得られる請求項 14記載の乳化組成物。 [15] The emulsified composition according to claim 14, obtained by the preparation method according to claim 11.
[16] 飲食品である請求項 14記載の乳化組成物。 [16] The emulsified composition according to claim 14, which is a food or drink.
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