WO2017090198A1 - Iron-containing powder composition - Google Patents

Iron-containing powder composition Download PDF

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Publication number
WO2017090198A1
WO2017090198A1 PCT/JP2015/083449 JP2015083449W WO2017090198A1 WO 2017090198 A1 WO2017090198 A1 WO 2017090198A1 JP 2015083449 W JP2015083449 W JP 2015083449W WO 2017090198 A1 WO2017090198 A1 WO 2017090198A1
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Prior art keywords
iron
mass
powder composition
containing powder
lecithin
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PCT/JP2015/083449
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French (fr)
Japanese (ja)
Inventor
篤史 加藤
貴之 田島
悦子 冨永
昌洋 黒野
Original Assignee
太陽化学株式会社
篤史 加藤
貴之 田島
悦子 冨永
昌洋 黒野
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Application filed by 太陽化学株式会社, 篤史 加藤, 貴之 田島, 悦子 冨永, 昌洋 黒野 filed Critical 太陽化学株式会社
Priority to PCT/JP2015/083449 priority Critical patent/WO2017090198A1/en
Publication of WO2017090198A1 publication Critical patent/WO2017090198A1/en

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    • 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
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16Inorganic salts, minerals or trace elements

Definitions

  • the present invention relates to an iron-containing powder composition suitable for supplementing iron in the food field, pharmaceutical field and the like.
  • Iron is known to exist in a state of being bound to hemoglobin, which is a protein in blood. When iron is deficient, it is supplemented by stored iron in the tissue. The lack of stored iron is called occult anemia and has become a global problem in developing and developed countries. In order to solve this shortage of iron, foods and pharmaceuticals with enhanced iron content have been sold. On the other hand, water-soluble iron has a high solubility, but its iron taste is very strong and has a great influence on the taste of the product, while water-insoluble iron improves the iron odor but has a high specific gravity. There is a problem that it is difficult to achieve homogenization. For this reason, various studies have been made on methods for adding to products.
  • Patent Document 1 with respect to 100 parts by mass of ferric pyrophosphate (A), 0.1 to 90 parts by mass of propylene glycol alginate (B), and at least selected from glycerin fatty acid ester, modified starch, and citrate It has been reported that when 0.1 to 90 parts by mass of one additive (C) is blended, redispersibility in the liquid, long-term dispersion stability in the liquid, and flavor are excellent.
  • ferric pyrophosphate A
  • B propylene glycol alginate
  • C one additive
  • composition containing (A) to (C) is used for a product that is stored for a long period of time
  • at least one additive selected from emulsifiers, polysaccharides, oligosaccharides, and amino acids It is disclosed that an embodiment in which 0.1 to 90 parts by mass of D) is further contained is preferable.
  • Patent Document 2 by using gati gum, a thickening stabilizer, as a water-insoluble iron salt, the water-insoluble iron salt is stably dispersed without aggregation even when stored for a long time.
  • iron-enhanced food / beverage composition that can maintain a good flavor of the food / beverage product itself without iron having a metallic taste can be provided.
  • Such an iron-reinforced food and drink composition is described as being prepared by mixing a water-insoluble iron salt and gati gum in a hydrophilic solvent such as water or polyhydric alcohol.
  • ferric pyrophosphate water It is disclosed that a solution obtained by mixing gati gum with a dispersion showed good dispersibility after storage at room temperature for 3 days.
  • a hydrophilic emulsifier is easy to peel and transfer to an aqueous phase once a film is formed, or has low biocompatibility with phospholipids and the like constituting a biological membrane, while phosphorous such as lecithin is low.
  • lipids are used as coatings, problems such as the formation of coarse particles due to secondary aggregation of primary fine particles caused by the charge of phospholipids were found.
  • salt fine particles metal fine particles
  • HLB relatively lipophilic emulsifier having an HLB of 6 to 10
  • Patent Document 4 discloses that enzyme-decomposed lecithin is used in order to provide a mineral composition that does not require a large amount of crystalline cellulose, fats and oils, has high heat stability, and is excellent in dispersibility. .
  • the iron absorbability is improved and excellent sustained release is expressed by orally administering a slurry of ferric pyrophosphate-enzymatically decomposed lecithin complex to rats. ing.
  • An object of the present invention is to provide an iron-containing powder composition having excellent long-term storage stability, and a food and drink and a pharmaceutical composition containing the composition.
  • the present invention relates to an iron-containing powder composition
  • an iron-containing powder composition comprising (A) ferric pyrophosphate, (B) lecithin, and (C) at least one selected from the group consisting of alginic acid, carboxymethylcellulose, and salts thereof. , Regarding.
  • the iron-containing powder composition of the present invention has an excellent effect that it can be stably dispersed even after long-term storage.
  • the iron-containing powder composition of the present invention contains (A) ferric pyrophosphate, (B) lecithin, and (C) at least one selected from the group consisting of alginic acid, carboxymethylcellulose, and salts thereof. It has the characteristics. Ferric pyrophosphate is a water-insoluble polyvalent metal salt, while lecithin has a charge on its side chain. Therefore, when ferric pyrophosphate and lecithin are mixed, as described in Patent Document 3, a chelate salt is formed by their charge, and the particles become enormous.
  • alginic acid is composed of D-mannuronic acid (M) and L-guluronic acid (G), which are constituent sugars of MM bonds with a three-dimensional left-handed helical structure and G with a two-dimensional screw-like straight chain structure.
  • any polysaccharide is a stable polymer. It has a network structure. Therefore, by using such a polysaccharide, it becomes possible to maintain the holding structure as described above more stably, and the binding of the main chain is stabilized in the long term due to the steric hindrance of the polysaccharide even in the powder state. Therefore, the aggregation of the primary particles is suppressed, and the stability of the particles in the powder state is improved.
  • the dispersion is good. It is inferred that sex can be obtained. Moreover, since lecithin is a main component of the biological membrane, it is considered that the biocompatibility is high and the bioavailability is also excellent.
  • the ferric pyrophosphate used in the present invention is not particularly limited, and may be synthesized according to a known method or may be a commercially available product.
  • the average particle size of ferric pyrophosphate used in the present invention is not particularly limited, but is preferably as fine as possible, preferably 1.0 ⁇ m or less, more preferably 0.7 ⁇ m or less, More preferably, it is 0.3 ⁇ m or less.
  • the lower limit is not particularly set, but is preferably 0.05 ⁇ m or more.
  • the volume median particle diameter of ferric pyrophosphate is preferably 0.8 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.2 ⁇ m or less, from the viewpoint of dispersion stability.
  • the lower limit is not particularly set, but is preferably 0.01 ⁇ m or more.
  • the ferric pyrophosphate particles used are not particularly limited even if they are larger than the particles of the obtained iron-containing powder composition in consideration of the method for preparing the iron-containing powder composition of the present invention.
  • the average particle size of fine particles is the average particle size of primary particles
  • the volume-median particle size is a cumulative curve obtained when the total volume of particles in the particle size distribution is 100%.
  • the cumulative curve is a particle size of 50%, and any of them can be measured according to a known method.
  • a laser diffraction / scattering method, a dynamic light scattering method, a sedimentation method, an image analysis method, or the like can be used. Of these, the laser diffraction / scattering method and the dynamic light scattering method are preferable from the viewpoint of measurement accuracy and simplicity.
  • a well-known method can be used.
  • a physical crushing method using a wet pulverizer such as a dyno mill, a sand mill, a coball mill, an emulsifier / disperser such as a nanomizer, a microfluidizer, a homogenizer, an ultrasonic disperser, etc. is preferable.
  • the method is more preferred.
  • the content of ferric pyrophosphate in the iron-containing powder composition of the present invention is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, further preferably 5.0% by mass or more, from the viewpoint of iron content. From the viewpoint of long-term stability, it is preferably 95% by mass or less, more preferably 75% by mass or less, and further preferably 60% by mass or less.
  • the lecithin used in the present invention comprises a glycerin skeleton, a fatty acid residue and a phosphate residue as essential components, and a base, a polyhydric alcohol and the like bound thereto, and is also referred to as a phospholipid.
  • Lecithin is defined by structural characteristics and solubility in toluene / acetone, but may be chemically a mixture of compounds.
  • Specific compounds include phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidic acid, lysophosphatidylcholine, phosphatidylglycerol, N-amylphosphatidylethanolamine, phosphatidylserine, lysophosphatidylethanolamine, etc. It may be a mixture of two or more.
  • the origin of lecithin is not particularly limited, and plant lecithin such as soybean, rapeseed, sunflower, and other oil seeds, eggs, and those obtained from the brain of animals can be used, but from the viewpoint of flavor and dispersibility, it is preferable. Good from rapeseed.
  • enzymatically decomposed lecithin can also be used as the lecithin.
  • the enzyme-degraded lecithin include, but are not limited to, those obtained by limited hydrolysis of fatty acid ester moieties with plant phosphotin or egg yolk lecithin with phospholipase.
  • lysophosphatidylcholine obtained using phospholipase A
  • lysophosphatidylethanolamine obtained using phospholipase A
  • lysophosphatidylinositol monoacylglycerophospholipids such as lysophosphatidylserine
  • phosphatidic acid obtained using phospholipase D
  • lyso examples thereof include phosphatidic acid, phosphatidylglycerol, and lysophosphatidylglycerol.
  • the above enzymatically decomposed lecithin may be used singly or in combination of two or more.
  • the enzyme-degraded lecithin used in the present invention is preferably one or more selected from the group consisting of lysophosphatidylcholine, lysophosphatidylethanolamine, and lysophosphatidylserine, more preferably from the viewpoints of flavor and dispersibility. Lysophosphatidylcholine.
  • the phospholipase used for enzymatic degradation has phospholipase A and / or D activity regardless of origin such as animal origin such as porcine pancreas, plant origin such as cabbage, or microbial origin such as mold. Any of them can be preferably used.
  • the amount of lecithin is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably from 100 parts by mass of ferric pyrophosphate from the viewpoint of particle surface adsorption. 0.05 parts by mass or more. From the viewpoint of flavor, it is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 8 parts by mass or less with respect to 100 parts by mass of ferric pyrophosphate.
  • the content of the component (B) in the iron-containing powder composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more from the viewpoint of dispersibility. From the viewpoint of flavor, it is preferably 10% by mass or less, more preferably 5.0% by mass or less, and further preferably 2.0% by mass or less.
  • Component (C) examples of the polysaccharide used in the present invention include alginic acid, carboxymethyl cellulose (CMC), and salts thereof.
  • the salt an alkali metal salt is preferable, and specific examples thereof include a sodium salt and a potassium salt.
  • the viscosity at 20 ° C. of alginic acid, CMC, and salts thereof is not particularly limited.
  • a 1% by mass aqueous solution it is preferably 1000 mPa ⁇ s from the viewpoint of solubility in water.
  • it is more preferably 500 mPa ⁇ s or less, and still more preferably 100 mPa ⁇ s or less.
  • measurement is performed as a 10% by mass aqueous solution.
  • the viscosity of component (C) can be measured using a B-type viscometer.
  • the amount of at least one selected from the group consisting of alginic acid, CMC, and salts thereof is preferably 0.5 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of ferric pyrophosphate from the viewpoint of the interparticle distance. 1.0 parts by mass or more, more preferably 5.0 parts by mass or more. From the viewpoint of production efficiency, the amount is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 100 parts by mass or less with respect to 100 parts by mass of ferric pyrophosphate.
  • the amount of at least one selected from the group consisting of alginic acid, CMC, and salts thereof means the total amount of alginic acid, CMC, and salts used, and is described as the amount of component (C). Sometimes.
  • the mass ratio [component (B) / component (C)] of lecithin and at least one selected from the group consisting of alginic acid, CMC, and salts thereof is 0.001 / 75 from the viewpoint of the interaction between lecithin and polysaccharide. To 5/1 is preferable, 0.01 / 40 to 2/5 is more preferable, and 0.05 / 25 to 1/10 is more preferable.
  • the content of the component (C) in the iron-containing powder composition of the present invention is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 3.0% by mass or more, from the viewpoint of suppressing secondary aggregation. From the viewpoint of solubility of the powder iron preparation, it is preferably 75% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.
  • the iron-containing powder composition of the present invention contains the components (A) to (C), but can contain other additives within a range not impairing the effects of the present invention.
  • the additive include other emulsifiers such as sorbitan fatty acid ester and sucrose fatty acid ester, and other excipients such as dextrin. These contents can be appropriately set based on known techniques.
  • dextrin is preferably used from the viewpoint of solubility in water.
  • the content of dextrin in the iron-containing powder composition of the present invention is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, and further preferably 10% by mass or more from the viewpoint of dispersibility. From the viewpoint of solubility in water, it is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
  • the method for preparing the iron-containing powder composition of the present invention is not particularly limited as long as it contains the components (A) to (C).
  • it can be obtained by uniformly mixing at least one selected from the group consisting of ferric pyrophosphate, lecithin, alginic acid, CMC, and salts thereof, and if necessary.
  • ferric pyrophosphate and lecithin form a complex in advance, and are prepared by mixing at least one selected from the group consisting of alginic acid, CMC, and salts thereof, and, if necessary, additives. May be.
  • the apparatus used for mixing is not particularly limited, and examples thereof include a powder dissolver, a homogenizer, a homodisper, a propeller mixer, and a stirrer. Moreover, you may use media, such as water and a solvent, at the time of the said raw material mixing, In that case, it pulverizes after mixing of a raw material.
  • the apparatus used for pulverization is not particularly limited, and examples thereof include a freeze dryer, a spray dryer, a slurry dryer, a drum dryer, and hot air drying.
  • the obtained powder may be used as it is, or may be made into fine particles according to a known method.
  • the apparatus used for atomization is as described above.
  • the mixing (stirring) time, temperature, intensity of mixing (stirring) and the like are not particularly limited, and may be set as appropriate according to the type of apparatus used.
  • the obtained iron-containing powder composition has an iron content of Even if 100 mL of the solution obtained by diluting with ion-exchanged water to a concentration of 10 mg / 100 mL is poured into a 100 mL Nessler tube and allowed to stand at room temperature for 1 day, precipitation does not occur at the bottom and separation occurs. It can be defined that it is not covered. This is because the coated particles do not aggregate and are stably dispersed in water. Further, the presence or absence of coating may be directly confirmed using an electron microscope or the like.
  • the average particle size of the obtained iron-containing powder composition is not particularly limited, but is preferably 0.8 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.2 ⁇ m or less from the viewpoint of dispersibility.
  • the lower limit is not particularly set, but is preferably 0.05 ⁇ m or more.
  • the volume median particle diameter is preferably 0.5 ⁇ m or less, more preferably 0.3 ⁇ m or less, and further preferably 0.15 ⁇ m or less from the viewpoint of dispersion stability.
  • the lower limit is not particularly set, but is preferably 0.01 ⁇ m or more.
  • the average particle diameter after storage at 65 ° C. for 3 days is preferably 1.0 ⁇ m or less, more preferably Is 0.6 ⁇ m or less, more preferably 0.3 ⁇ m or less.
  • the lower limit is not particularly set, but is preferably 0.05 ⁇ m or more.
  • the volume-median particle diameter when stored in the same manner is preferably 0.8 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the lower limit is not particularly set, but is preferably 0.01 ⁇ m or more.
  • the average particle size after storage at 65 ° C. for 3 days The rate of change is preferably within ⁇ 400%, more preferably within ⁇ 200%, and even more preferably within ⁇ 100%.
  • the rate of change of the volume-median particle diameter after storage at 65 ° C. for 3 days is preferably within ⁇ 400%, more preferably ⁇ 200%. Within 100%, more preferably within ⁇ 100%.
  • the iron-containing composition of the present invention is in a powder form, and its use is not particularly limited as long as the composition can be taken into the body. It can be used for replenishment or maintenance of iron. For example, it is preferably used for iron deficiency anemia, sports anemia, and the like.
  • the amount of the iron-containing powder composition of the present invention is appropriately set according to the method of use, the purpose of use and the age, weight, and symptom of the user of the composition, but for example, the amount of iron is 7.5 mg.
  • the amount of daily intake is the preferred intake. Within a desired use amount range, it may be used once or multiple times within a day, and the use time and period are arbitrary.
  • the subject of the iron-containing powder composition of the present invention is preferably a human who needs supplementation or maintenance of iron content, but domestic animals such as cattle, horses and goats, and pet animals such as dogs, cats and rabbits. Or laboratory animals, such as a mouse
  • the iron-containing powder composition of the present invention is excellent in long-term storage stability, it can be satisfactorily dispersed in the product without exhibiting an unpleasant taste or flavor even after long-term storage. It is suitably used as a product or a raw material thereof.
  • the food and drink are not particularly limited as long as the iron-containing powder composition of the present invention is contained, and examples thereof include food and drink for supplying or maintaining iron.
  • foods for specified health use functional nutritional foods, foods for the elderly, special-purpose foods, functional foods, health supplements (supplements), for example, to be used to supplement or maintain iron It will be possible to provide it with the display.
  • Such foods and drinks include instant noodles, cup noodles, retort / cooked food, cooked canned food, microwave food, instant soup / stew, instant miso soup / soup, canned soup, freeze-dried food, carbonated drinks, Natural fruit juice, fruit juice drink, soft drink (including fruit juice), fruit drink, fruit food with fruit granules, vegetable drink, soy milk / soy milk drink, coffee drink, tea drink, powdered drink, concentrated drink, sports drink, nutrition Beverages, beverages such as alcoholic beverages, bread, macaroni / spaghetti, noodles, cake mix, fried flour / bread crumbs, gyoza / spring rolls and other flour foods, caramel candy, chewing gum, chocolate, cookies / biscuits, Cake pie, snack cracker, Japanese confectionery, rice confectionery, bean confectionery, baked confectionery, jelly, pudding, Confectionery such as baloa, dessert confectionery, soy sauce, miso, sauces, tomato processing seasoning, mirin, vinegar, sweetener, fish sauce, nyokumam and other basic season
  • a pharmaceutical composition it can be widely used as a medicine, a quasi-drug, and the like.
  • it can be used for the treatment or prevention of any disease for which supplementation or maintenance of iron is desired.
  • it can be suitably used for the treatment and prevention of iron deficiency anemia and sports anemia.
  • the pharmaceutical composition of the present invention can be prepared by blending together other components having the same action as the iron-containing powder composition of the present invention.
  • the form of the pharmaceutical composition is not particularly limited as long as it contains the iron-containing powder composition of the present invention.
  • powders, powders, fine granules, granules, pills, capsules Tablets [including uncoated tablets, sugar-coated tablets, intraoral quick disintegrating tablets, chewable tablets (chewable tablets), effervescent tablets, troches, film-coated tablets, etc.], dry syrups, films, liquids (suspensions, emulsions, Examples include syrups, limonades, etc.], jelly agents, and confectionery agents (candy, gummy, nougat agents, etc.).
  • the capsule includes a soft capsule filled with a solution in which the iron-containing powder composition of the present invention is dispersed.
  • the food and drink of the present invention and the pharmaceutical composition of the present invention include carriers, bases, and / or additives that are usually used in the pharmaceutical field and food field. It can be prepared by appropriately blending within the range of achieving the object of the present invention.
  • the content of the iron-containing powder composition of the present invention in these food and drink products and pharmaceutical compositions is the preferred use amount of the iron-containing powder composition of the present invention described above, for example, the amount of iron is 7.5 mg or more / It is the amount that makes up a day, and can be appropriately set according to a conventional method.
  • particle size distribution The particle size distribution is measured with a laser diffraction particle size distribution analyzer (trade name: LS 13 320, manufactured by BECKMAN COULTER), and the average particle size and the volume median particle size are determined.
  • ⁇ viscosity Prepare a 1 or 10% by weight aqueous solution in which the sample is dissolved in water, hold it at 20 ° C for 30 minutes, and then measure the viscosity under the following conditions (if measurement at 1% by weight is impossible, 10% by weight To make measurements).
  • Viscometer Brookfield viscometer BLII Measurement temperature: 20 °C
  • Examples 1 to 7 and Comparative Examples 1 to 11 An iron solution was prepared by dissolving 13 kg of ferric chloride hexahydrate in 45 kg of ion exchange water. Next, the iron solution obtained above was gradually added to a pyrophosphoric acid solution obtained by dissolving 16.5 kg of tetrasodium pyrophosphate (decahydrate) in 105 kg of ion-exchanged water. After the ferric pyrophosphate salt formation by the neutralization reaction is completed, the supernatant is removed by centrifugation (3000 ⁇ g, 10 minutes), ion-exchanged water is added to the resulting precipitate, and the mixture is stirred again. The precipitate was washed by centrifugation (3000 ⁇ g, 10 minutes).
  • the amount of lecithin / enzymatically decomposed lecithin with respect to 100 parts by mass of ferric pyrophosphate is 0.50 parts by mass
  • the amount of polysaccharide with respect to 100 parts by mass of ferric pyrophosphate is 70 parts by mass
  • the mass of emulsifier and polysaccharide The ratio (emulsifier / polysaccharide) was 0.5 / 70.
  • the amount of dextrin was 155 parts by mass with respect to 100 parts by mass of ferric pyrophosphate.
  • Lecithin is trade name “ADLEC RL” (manufactured by ADM)
  • enzyme-degraded lecithin is trade name “Sun lecithin L” (manufactured by Taiyo Kagaku)
  • sodium alginate is trade name “Kimika Argin” (manufactured by Kimika Corporation, 20 Viscosity of 1% by mass at 30 ° C., 30 mPa ⁇ s, hereinafter referred to as sodium alginate A)
  • trade name “Kimika Algin” manufactured by Kimika, 1 mass% of viscosity at 20 ° C., 300 mPa ⁇ s, hereinafter referred to as sodium alginate)
  • Trade name “Kimika Argin” (Kimika Corp., 1 mass% viscosity at 20 ° C.
  • sodium alginate C 600 mPa ⁇ s, hereinafter referred to as sodium alginate C), and trade name “Kimika Argin” (Kimika Corp., 10 ° C. at 10 ° C. Viscosity of 40 mPa ⁇ s in mass%, hereinafter referred to as sodium alginate D), sodium carboxymethylcellulose is trade name “Serogen” (Daiichi Kogyo Seiyaku Co., Ltd., 1 mass% viscosity of 40 mPa at 20 ° C.) s) was used.
  • Test example 1 The obtained powder composition, which was sealed in an aluminum laminate bag, was stored in a constant temperature room at 65 ° C., sampled over time, and the average particle size and volume median particle size were measured. The results are shown in Tables 1 and 2. In addition, for the composition whose average particle size and volume median particle size at the time of measurement exceeded 1 ⁇ m, the subsequent sampling was not performed, and it was indicated by “---” in the table.
  • Comparative Examples 1 and 2 did not contain polysaccharides, aggregation of secondary particles of ferric pyrophosphate could not be suppressed during preparation. Since Comparative Example 3 did not contain lecithin, the interaction between ferric pyrophosphate and sodium alginate was weak and aggregation during powder was suppressed, but redispersibility could not be maintained in the long term. .
  • Table 1 suggests that in Examples 1 to 7, the main chain of the polysaccharide is difficult to be decomposed, secondary aggregation is hardly caused even by excessive heat, and excellent long-term stability in a powder state. .
  • Examples 2 to 5 using sodium alginate having different viscosities no large difference was observed in the particle diameter after storage. Although there was a slight difference in the particle size depending on the presence or absence of dextrin, there was no essential difference.
  • Test example 2 For the samples stored at 65 ° C. for 3 days in Examples 1 to 7, 100 mL of a solution obtained by diluting with iron-exchanged water so that the iron content was 10 mg / 100 mL was poured into a 100 mL Nessler tube at room temperature. Left at rest.
  • Example 4 (example using sodium alginate C) showed good dispersibility once dissolved or dispersed, the solubility of the powder was somewhat poor, and it took time to dissolve.
  • Test example 3 200 g of ferric pyrophosphate prepared with reference to Example 1 was mixed and dispersed in 1800 g of ion-exchanged water, and this dispersion was wet pulverized by a wet pulverizer Dynomill. A ferric pyrophosphate slurry containing 5% by mass was obtained (average particle size of ferric pyrophosphate 0.268 ⁇ m, volume median particle size 0.197 ⁇ m). A powder composition of Example 8 was prepared by spray drying after adding 0.0105 g of lecithin, 2.55 g of sodium alginate A, and 4.2 g of dextrin to 30 g of the slurry product.
  • the amount of lecithin relative to 100 parts by mass of ferric pyrophosphate was 0.35 parts by mass, the amount of sodium alginate was 85 parts by mass, and the mass ratio of emulsifier to polysaccharide (emulsifier / polysaccharide) was 0.1 / 24.
  • the amount of dextrin was 140 parts by mass with respect to 100 parts by mass of ferric pyrophosphate.
  • Comparative Examples 4 to 11 using polysaccharides other than alginic acid and Comparative Example 3 to which no lecithin was added produced secondary agglomeration after storage at 65 ° C. for 6 days.
  • the change rate of the particle size was within ⁇ 100% even after 12 months from 65 ° C for 1 month, 55 ° C for 2 months, 42 ° C, 37 ° C and 25 ° C. It was.
  • Test example 4 Implementation was carried out in the same manner as the powder composition of Example 6 except that the amount used was changed so that the mass ratio of lecithin, sodium alginate A, and dextrin to 100 parts by mass of ferric pyrophosphate was the amount shown in Table 4.
  • the powder compositions of Examples 9-10 were prepared.
  • Example 9 since the ratio of lecithin is small, dispersibility and stability are slightly deteriorated, but the dispersibility is maintained for a certain period even when stored at 65 ° C. Moreover, in Example 10, since the ratio of alginic acid is small, the stability is slightly deteriorated, but the dispersibility is maintained for a certain period even when stored at 65 ° C.
  • Iron-enhanced soft drink 750 mL of ion-exchange water, 100 g of fructose glucose liquid sugar, 2.0 g of citric acid, 0.5 g of sodium citrate, 0.75 g of the iron-containing powder composition obtained in Example 1, an appropriate amount of flavor, and an appropriate amount of colorant
  • ion-exchanged water is added to adjust to 1000 mL, and then 100 mL is filled into bottles and sterilized by heating at 90 ° C. for 10 minutes to prepare an iron-reinforced soft drink.
  • Iron-enriched milk beverage 0.2 g of the iron-containing powder composition of the present invention is dissolved in 882 mL of ion-exchanged water, 89.2 g of skim milk powder is added, and homogenized with a homomixer. Thereafter, 28.6 g of fresh cream is added, and after mixing, ion-exchanged water is added to adjust to 1000 mL, and then 200 mL each is packed in a bottle and sterilized at 63 ° C. for 30 minutes to obtain an iron-enriched milk beverage.
  • the iron-containing powder composition of the present invention can be stably dispersed even after long-term storage, it is suitably used for foods and drinks and pharmaceuticals as an iron supplement, having substantially no influence on taste, color, physical properties, etc. can do.

Abstract

An iron-containing powder composition which contains (A) iron(III) pyrophosphate, (B) lecithin and (C) at least one substance selected from the group consisting of alginic acid, carboxymethyl cellulose and salts of alginic acid or carboxymethyl cellulose; and food, drink and a pharmaceutical composition, each of which contains this composition. Since an iron-containing powder composition according to the present invention is able to be stably dispersed even after long-term storage, this iron-containing powder composition is suitable for use in food, drink or a pharmaceutical product as an iron supplement which has no substantial influence on taste, color, physical properties and the like.

Description

鉄含有粉末組成物Iron-containing powder composition
 本発明は、食品分野、医薬品分野等で鉄分を補給するのに好適な鉄含有粉末組成物に関する。 The present invention relates to an iron-containing powder composition suitable for supplementing iron in the food field, pharmaceutical field and the like.
 鉄は、血中のタンパク質であるヘモグロビンに結合した状態で存在することが知られており、鉄不足の状態になると組織中の貯蔵鉄から補われる。貯蔵鉄が不足した状態は潜在性貧血症と呼ばれ、発展途上国から先進国において世界的な問題となっている。この鉄不足を解消する為に、鉄分を強化した食品・医薬品等が販売されるようになってきている。一方で、水溶性の鉄は溶解性は高いが鉄味が非常に強く製品の呈味に大きな影響を与えたり、水不溶性の鉄は鉄臭は改善されるものの比重が高いことから製品中での均質化を図ることが困難であるといった問題がある。そのため、製品への添加方法に関して様々な研究がなされている。 Iron is known to exist in a state of being bound to hemoglobin, which is a protein in blood. When iron is deficient, it is supplemented by stored iron in the tissue. The lack of stored iron is called occult anemia and has become a global problem in developing and developed countries. In order to solve this shortage of iron, foods and pharmaceuticals with enhanced iron content have been sold. On the other hand, water-soluble iron has a high solubility, but its iron taste is very strong and has a great influence on the taste of the product, while water-insoluble iron improves the iron odor but has a high specific gravity. There is a problem that it is difficult to achieve homogenization. For this reason, various studies have been made on methods for adding to products.
 例えば、添加剤によって水不溶性鉄の分散性を向上させる方法が挙げられる。特許文献1では、ピロリン酸第二鉄(A)100質量部に対し、アルギン酸プロピレングリコールエステル(B)を0.1~90質量部、及び、グリセリン脂肪酸エステル、加工デンプン、クエン酸塩より選ばれた少なくとも1種の添加剤(C)を0.1~90質量部配合したところ、液中での再分散性、液中での長期分散安定性、ならびに風味が優れるようになったことが報告されている。また、前記(A)~(C)を含有する組成物を長期間保存するような製品に使用する場合には、乳化剤、多糖類、少糖、アミノ酸より選ばれた少なくとも1種の添加剤(D)を0.1~90質量部さらに含有させる態様が好適であることが開示されている。 For example, a method of improving the dispersibility of water-insoluble iron with an additive can be mentioned. In Patent Document 1, with respect to 100 parts by mass of ferric pyrophosphate (A), 0.1 to 90 parts by mass of propylene glycol alginate (B), and at least selected from glycerin fatty acid ester, modified starch, and citrate It has been reported that when 0.1 to 90 parts by mass of one additive (C) is blended, redispersibility in the liquid, long-term dispersion stability in the liquid, and flavor are excellent. When the composition containing (A) to (C) is used for a product that is stored for a long period of time, at least one additive selected from emulsifiers, polysaccharides, oligosaccharides, and amino acids ( It is disclosed that an embodiment in which 0.1 to 90 parts by mass of D) is further contained is preferable.
 また、微粒子化によって分散性を向上させる方法も挙げられるが、数ミクロンオーダーの微細化では十分な分散安定性が得られなかったり、超微粒子とした場合には二次凝集が生じて粗大粒子が形成するなどの問題がある。そこで、微粒子表面を有機酸やアルカリ剤、界面活性剤で処理する方法、親水性の乳化剤と共に湿式粉砕する方法などが検討されている。 In addition, there is a method of improving dispersibility by making fine particles, but sufficient dispersion stability cannot be obtained by miniaturization on the order of several microns, or secondary particles are formed in the case of ultrafine particles, resulting in coarse particles. There are problems such as forming. Therefore, a method of treating the surface of fine particles with an organic acid, an alkali agent or a surfactant, a method of wet pulverizing with a hydrophilic emulsifier, and the like have been studied.
 例えば、特許文献2では、水不溶性鉄塩に、増粘安定剤のガティガムを用いることにより、水不溶性鉄塩を長時間保存しても凝集することなく安定に分散し、更には飲食品中で鉄が金属味を呈することなく、飲食品自体の良好な風味を維持可能とした鉄強化飲食品用組成物を提供できることが報告されている。かかる鉄強化飲食品用組成物としては、水や多価アルコール等の親水性溶媒に水不溶性鉄塩とガティガムを混合して調製すると記載されており、実施例では、ピロリン酸第二鉄の水分散液にガティガムを混合した溶液が、常温で3日間保存後に良好な分散性を示したことが開示されている。 For example, in Patent Document 2, by using gati gum, a thickening stabilizer, as a water-insoluble iron salt, the water-insoluble iron salt is stably dispersed without aggregation even when stored for a long time. It has been reported that iron-enhanced food / beverage composition that can maintain a good flavor of the food / beverage product itself without iron having a metallic taste can be provided. Such an iron-reinforced food and drink composition is described as being prepared by mixing a water-insoluble iron salt and gati gum in a hydrophilic solvent such as water or polyhydric alcohol. In the examples, ferric pyrophosphate water It is disclosed that a solution obtained by mixing gati gum with a dispersion showed good dispersibility after storage at room temperature for 3 days.
 特許文献3では、親水性の乳化剤は、被膜が一旦形成されても水相へ剥離移行しやすかったり、生体膜を構成するリン脂質等との生体親和性が低く、一方で、レシチン等のリン脂質を被膜に用いると、リン脂質の電荷によって一次微粒子の二次凝集が生じて粗大粒子が形成される等の問題が見出されたことなどから、微小な平均粒子径を有する水不溶性の金属塩類の微粒子(金属微粒子)に、HLBが6~10の比較的親油性の乳化剤によって吸着層を形成することで、金属微粒子の二次凝集が抑制され、食品や飲料に添加した際には良好な分散性が得られ、生体利用率にも優れると開示されている。また、実施例では、ピロリン酸第二鉄の水分散液に、ジグリセリン脂肪酸エステル等の乳化剤を混合した組成物が、室温で3か月保存後に、成分の分離や沈殿の発生がなく良好な保存安定性を示すことが報告されている。 In Patent Document 3, a hydrophilic emulsifier is easy to peel and transfer to an aqueous phase once a film is formed, or has low biocompatibility with phospholipids and the like constituting a biological membrane, while phosphorous such as lecithin is low. When lipids are used as coatings, problems such as the formation of coarse particles due to secondary aggregation of primary fine particles caused by the charge of phospholipids were found. By forming an adsorption layer on salt fine particles (metal fine particles) with a relatively lipophilic emulsifier having an HLB of 6 to 10, secondary aggregation of metal fine particles is suppressed, which is good when added to foods and beverages. It is disclosed that excellent dispersibility can be obtained and the bioavailability is also excellent. Also, in the examples, a composition in which an emulsifier such as diglycerin fatty acid ester is mixed with an aqueous dispersion of ferric pyrophosphate, and after storage at room temperature for 3 months, there is no occurrence of separation of components or precipitation. It has been reported to show storage stability.
 また、特許文献4では、結晶セルロースや油脂などを多量に必要とせず、加熱安定性が高く、分散性に優れたミネラル組成物を提供するために、酵素分解レシチンを用いることが開示されている。例えば、実施例では、ピロリン酸第二鉄-酵素分解レシチン複合体のスラリーをラットに経口投与することで、鉄の吸収性が向上し、優れた徐放性が発現されていることが記載されている。 Patent Document 4 discloses that enzyme-decomposed lecithin is used in order to provide a mineral composition that does not require a large amount of crystalline cellulose, fats and oils, has high heat stability, and is excellent in dispersibility. . For example, in the Examples, it is described that the iron absorbability is improved and excellent sustained release is expressed by orally administering a slurry of ferric pyrophosphate-enzymatically decomposed lecithin complex to rats. ing.
WO2004/039178号公報WO2004 / 039178 特開2009-89634号公報JP 2009-89634 A 特許第4410757号公報Japanese Patent No. 4410757 WO98/14072号公報WO98 / 14072 Publication
 しかしながら、従来提案された技術はそれなりの成果はあるものの、近年の需要拡大に伴って飲食品等に添加する前の状態での品質の向上がより求められ、特に微細分散する粉末状の長期安定性を有する鉄含有組成物が求められている。 However, although the conventionally proposed technology has some results, it is required to improve the quality before adding to foods and drinks with the recent increase in demand, especially in the long-term stable state of finely dispersed powder. There is a need for iron-containing compositions having properties.
 本発明の課題は、長期保存安定性に優れる鉄含有粉末組成物、及び該組成物を含有する飲食品、医薬組成物を提供することにある。 An object of the present invention is to provide an iron-containing powder composition having excellent long-term storage stability, and a food and drink and a pharmaceutical composition containing the composition.
 本発明は、(A)ピロリン酸第二鉄、(B)レシチン、ならびに(C)アルギン酸、カルボキシメチルセルロース、及びそれらの塩からなる群より選ばれる少なくとも1種を含有してなる鉄含有粉末組成物、に関する。 The present invention relates to an iron-containing powder composition comprising (A) ferric pyrophosphate, (B) lecithin, and (C) at least one selected from the group consisting of alginic acid, carboxymethylcellulose, and salts thereof. , Regarding.
 本発明の鉄含有粉末組成物は、長期間保存後でも、安定に分散させることができるという優れた効果を奏するものである。 The iron-containing powder composition of the present invention has an excellent effect that it can be stably dispersed even after long-term storage.
 本発明の鉄含有粉末組成物は、(A)ピロリン酸第二鉄、(B)レシチン、ならびに(C)アルギン酸、カルボキシメチルセルロース、及びそれらの塩からなる群より選ばれる少なくとも1種を含有することに特徴を有する。ピロリン酸第二鉄は水不溶性の多価金属塩であり、一方、レシチンはその側鎖に電荷を有するものである。よって、ピロリン酸第二鉄とレシチンを混合すると、特許文献3に記載のように、それらの電荷によってキレート塩が形成されて粒子が巨大化することになる。しかしながら、そこに特定の多糖類をさらに存在させることで、詳細なる理由は不明なるも、得られる微粒子は、レシチンによって被覆されたピロリン酸第二鉄が、多糖類の電荷によってその高分子網目構造中に安定に良分散が保持された構造を有することになる。また、アルギン酸はその構成糖であるD-マンヌロン酸(M)及びL-グルロン酸(G)が、3次元の左巻きらせん構造を持つM-M結合や2次元のねじ状直鎖構造を持つG-G結合を形成するために、あるいは、カルボキシメチルセルロースは50~60℃程度の加熱では可逆的な粘度の変化が起こるだけで加熱による特性変動が小さいために、いずれの多糖類も安定な高分子網目構造を有するものである。よって、かかる多糖類を用いることで、前記のような保持構造をより安定に維持することが可能となり、粉末状態であっても多糖類が持つ立体障害により主鎖の結合が長期的に安定化されることから一次粒子の凝集が抑制されることになって、該粒子の粉末状態での安定性が良好になり、ひいては該粉末微粒子を飲食品や医薬組成物に分散させても良好な分散性が得られると推察される。また、レシチンが生体膜の主要構成成分であることから、生体親和性が高く、生体利用率にも優れると考えられる。 The iron-containing powder composition of the present invention contains (A) ferric pyrophosphate, (B) lecithin, and (C) at least one selected from the group consisting of alginic acid, carboxymethylcellulose, and salts thereof. It has the characteristics. Ferric pyrophosphate is a water-insoluble polyvalent metal salt, while lecithin has a charge on its side chain. Therefore, when ferric pyrophosphate and lecithin are mixed, as described in Patent Document 3, a chelate salt is formed by their charge, and the particles become enormous. However, the detailed reason is unclear when the specific polysaccharide is further present there, but the fine particles obtained are ferric pyrophosphate coated with lecithin, the polymer network structure due to the charge of the polysaccharide. It has a structure in which good dispersion is stably maintained. In addition, alginic acid is composed of D-mannuronic acid (M) and L-guluronic acid (G), which are constituent sugars of MM bonds with a three-dimensional left-handed helical structure and G with a two-dimensional screw-like straight chain structure. -Since carboxymethylcellulose is a reversible viscosity change when heated to about 50-60 ° C to form a G bond, or the property variation due to heating is small, any polysaccharide is a stable polymer. It has a network structure. Therefore, by using such a polysaccharide, it becomes possible to maintain the holding structure as described above more stably, and the binding of the main chain is stabilized in the long term due to the steric hindrance of the polysaccharide even in the powder state. Therefore, the aggregation of the primary particles is suppressed, and the stability of the particles in the powder state is improved. As a result, even if the powder fine particles are dispersed in a food or drink or a pharmaceutical composition, the dispersion is good. It is inferred that sex can be obtained. Moreover, since lecithin is a main component of the biological membrane, it is considered that the biocompatibility is high and the bioavailability is also excellent.
〔成分(A)〕
 本発明で用いられるピロリン酸第二鉄としては、特に制限はなく、公知の方法に従って合成したものであっても、市販品であってもよい。
[Component (A)]
The ferric pyrophosphate used in the present invention is not particularly limited, and may be synthesized according to a known method or may be a commercially available product.
 本発明で用いられるピロリン酸第二鉄の平均粒子径は、特に限定されるものではないが、出来るだけ微粒子化されたものが好ましいことから、好ましくは1.0μm以下、より好ましくは0.7μm以下、さらに好ましくは0.3μm以下である。下限値は特に設定されないが、0.05μm以上が好ましい。また、ピロリン酸第二鉄の体積中位粒子径は、分散安定性の観点から、好ましくは0.8μm以下、より好ましくは0.5μm以下、さらに好ましくは0.2μm以下である。下限値は特に設定されないが、0.01μm以上が好ましい。なお、用いられるピロリン酸第二鉄の粒子は、本発明の鉄含有粉末組成物の調製方法を考慮して、得られる鉄含有粉末組成物の粒子より大きいものであっても特に制限されない。本明細書において、微粒子の平均粒子径とは一次粒子の平均粒子径のことであり、体積中位粒子径とは粒径分布における粒子の集団の全体積を100%として累積カーブを求めたとき、その累積カーブが50%の粒子径のことであり、いずれも公知の方法に従って測定することができる。例えば、レーザー回折・散乱法、動的光散乱法、沈降法、画像解析法などを用いることができる。なかでも、測定精度及び簡便性の観点から、レーザー回折・散乱法、動的光散乱法が好ましい。 The average particle size of ferric pyrophosphate used in the present invention is not particularly limited, but is preferably as fine as possible, preferably 1.0 μm or less, more preferably 0.7 μm or less, More preferably, it is 0.3 μm or less. The lower limit is not particularly set, but is preferably 0.05 μm or more. The volume median particle diameter of ferric pyrophosphate is preferably 0.8 μm or less, more preferably 0.5 μm or less, and still more preferably 0.2 μm or less, from the viewpoint of dispersion stability. The lower limit is not particularly set, but is preferably 0.01 μm or more. The ferric pyrophosphate particles used are not particularly limited even if they are larger than the particles of the obtained iron-containing powder composition in consideration of the method for preparing the iron-containing powder composition of the present invention. In this specification, the average particle size of fine particles is the average particle size of primary particles, and the volume-median particle size is a cumulative curve obtained when the total volume of particles in the particle size distribution is 100%. The cumulative curve is a particle size of 50%, and any of them can be measured according to a known method. For example, a laser diffraction / scattering method, a dynamic light scattering method, a sedimentation method, an image analysis method, or the like can be used. Of these, the laser diffraction / scattering method and the dynamic light scattering method are preferable from the viewpoint of measurement accuracy and simplicity.
 ピロリン酸第二鉄を微粒子化する方法としては、特に制限はなく、公知の方法を用いることができる。例えば、ダイノミル、サンドミル、コボールミル等の湿式粉砕機、ナノマイザー、マイクロフルイタイザー、ホモジナイザー等の乳化・分散装置、超音波分散機等を用いた物理的破砕法が好ましく、粒度調整の観点から、湿式粉砕法がより好ましい。 There is no restriction | limiting in particular as a method of micronizing ferric pyrophosphate, A well-known method can be used. For example, a physical crushing method using a wet pulverizer such as a dyno mill, a sand mill, a coball mill, an emulsifier / disperser such as a nanomizer, a microfluidizer, a homogenizer, an ultrasonic disperser, etc. is preferable. The method is more preferred.
 本発明の鉄含有粉末組成物におけるピロリン酸第二鉄の含有量は、鉄含量の観点から、好ましくは0.1質量%以上、より好ましくは1.0質量%以上、さらに好ましくは5.0質量%以上であり、長期安定性の観点から、好ましくは95質量%以下、より好ましくは75質量%以下、さらに好ましくは60質量%以下である。 The content of ferric pyrophosphate in the iron-containing powder composition of the present invention is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, further preferably 5.0% by mass or more, from the viewpoint of iron content. From the viewpoint of long-term stability, it is preferably 95% by mass or less, more preferably 75% by mass or less, and further preferably 60% by mass or less.
〔成分(B)〕
 本発明で用いられるレシチンとは、グリセリン骨格と脂肪酸残基及びリン酸残基を必須構成成分とし、これに塩基や多価アルコール等が結合したもので、リン脂質とも称される。なお、レシチンは構造的特徴やトルエン・アセトンに対する溶解性で定義されるが、化学的には化合物の混合物であってもよい。具体的な化合物としては、ホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルイノシトール、ホスファチジン酸、リゾホスファチジルコリン、ホスファチジルグリセロール、N-アミルホスファチジルエタノールアミン、ホスファチジルセリン、リゾホスファチジルエタノールアミン等が挙げられ、これらは1種単独であっても、2種以上の混合物であってもよい。なお、レシチンの起源は特に問わず、大豆、ナタネ、ひまわり、その他油糧種子等の植物レシチンや、卵、動物の脳から得られたものが使用できるが、風味、分散性の観点から好ましくはナタネから得られたものがよい。
[Component (B)]
The lecithin used in the present invention comprises a glycerin skeleton, a fatty acid residue and a phosphate residue as essential components, and a base, a polyhydric alcohol and the like bound thereto, and is also referred to as a phospholipid. Lecithin is defined by structural characteristics and solubility in toluene / acetone, but may be chemically a mixture of compounds. Specific compounds include phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidic acid, lysophosphatidylcholine, phosphatidylglycerol, N-amylphosphatidylethanolamine, phosphatidylserine, lysophosphatidylethanolamine, etc. It may be a mixture of two or more. The origin of lecithin is not particularly limited, and plant lecithin such as soybean, rapeseed, sunflower, and other oil seeds, eggs, and those obtained from the brain of animals can be used, but from the viewpoint of flavor and dispersibility, it is preferable. Good from rapeseed.
 また、本発明では、前記レシチンとして酵素分解レシチンも用いることができる。酵素分解レシチンとしては、例えば、植物レシチン又は卵黄レシチンをホスホリパーゼによって脂肪酸エステル部分を限定的に加水分解する事で得られるものが挙げられるが、これらに限定されない。具体的には、例えば、ホスホリパーゼAを用いて得られるリゾホスファチジルコリン、リゾホスファチジルエタノールアミン、リゾホスファチジルイノシートル、リゾホスファチジルセリン等のモノアシルグリセロリン脂質、及びホスホリパーゼDを用いて得られるホスファチジル酸、リゾホスファチジン酸、ホスファチジルグリセロール、リゾホスファチジルグリセロール等が挙げられる。本発明に用いられる酵素分解レシチンとしては、上記のような酵素分解レシチンを1種で用いてもよく、また、2種以上を組み合わせて用いてもよい。本発明に用いられる酵素分解レシチンとしては、風味、分散性の観点から好ましくはリゾホスファチジルコリン、リゾホスファチジルエタノールアミン、リゾホスファチジルセリンからなる群より選択される1種又は2種以上であり、より好ましくは、リゾホスファチジルコリンである。 In the present invention, enzymatically decomposed lecithin can also be used as the lecithin. Examples of the enzyme-degraded lecithin include, but are not limited to, those obtained by limited hydrolysis of fatty acid ester moieties with plant phosphotin or egg yolk lecithin with phospholipase. Specifically, for example, lysophosphatidylcholine obtained using phospholipase A, lysophosphatidylethanolamine, lysophosphatidylinositol, monoacylglycerophospholipids such as lysophosphatidylserine, and phosphatidic acid obtained using phospholipase D, lyso Examples thereof include phosphatidic acid, phosphatidylglycerol, and lysophosphatidylglycerol. As the enzymatically decomposed lecithin used in the present invention, the above enzymatically decomposed lecithin may be used singly or in combination of two or more. The enzyme-degraded lecithin used in the present invention is preferably one or more selected from the group consisting of lysophosphatidylcholine, lysophosphatidylethanolamine, and lysophosphatidylserine, more preferably from the viewpoints of flavor and dispersibility. Lysophosphatidylcholine.
 酵素分解レシチンの製造に際し、酵素分解に用いるホスホリパーゼとしては、豚膵臓等の動物起源、キャベツ等の植物起源、又はカビ類等の微生物起源等の由来を問わず、ホスホリパーゼA及び/又はD活性を有したものであればいずれも好ましく使用できる。 In the production of enzymatically degraded lecithin, the phospholipase used for enzymatic degradation has phospholipase A and / or D activity regardless of origin such as animal origin such as porcine pancreas, plant origin such as cabbage, or microbial origin such as mold. Any of them can be preferably used.
 レシチンの量〔成分(B)の量〕は、粒子表面吸着の観点から、ピロリン酸第二鉄100質量部に対して、好ましくは0.001質量部以上、より好ましくは0.01質量部以上、さらに好ましくは0.05質量部以上である。また、風味の観点から、ピロリン酸第二鉄100質量部に対して、好ましくは40質量部以下、より好ましくは20質量部以下、さらに好ましくは8質量部以下である。 The amount of lecithin [the amount of component (B)] is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably from 100 parts by mass of ferric pyrophosphate from the viewpoint of particle surface adsorption. 0.05 parts by mass or more. From the viewpoint of flavor, it is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 8 parts by mass or less with respect to 100 parts by mass of ferric pyrophosphate.
 また、本発明の鉄含有粉末組成物における成分(B)の含有量は、分散性の観点から、好ましくは0.001質量%以上、より好ましくは0.01質量%以上、さらに好ましくは0.05質量%以上であり、風味の観点から、好ましくは10質量%以下、より好ましくは5.0質量%以下、さらに好ましくは2.0質量%以下である。 In addition, the content of the component (B) in the iron-containing powder composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more from the viewpoint of dispersibility. From the viewpoint of flavor, it is preferably 10% by mass or less, more preferably 5.0% by mass or less, and further preferably 2.0% by mass or less.
〔成分(C)〕
 本発明で用いられる多糖類としては、アルギン酸、カルボキシメチルセルロース(CMC)、及びそれらの塩が挙げられる。塩としてはアルカリ金属塩が好ましく、具体的には、ナトリウム塩、カリウム塩が挙げられる。
[Component (C)]
Examples of the polysaccharide used in the present invention include alginic acid, carboxymethyl cellulose (CMC), and salts thereof. As the salt, an alkali metal salt is preferable, and specific examples thereof include a sodium salt and a potassium salt.
 アルギン酸、CMC、及びそれらの塩の20℃における粘度としては、特に限定されるものではないが、例えば、1質量%の水溶液とした場合、水への溶解性の観点から、好ましくは1000mPa・s以下、より好ましくは500mPa・s以下、さらに好ましくは100mPa・s以下である。また、1質量%の水溶液では測定が不能となる場合は、10質量%の水溶液として測定を行い、その場合、安定性の観点から、好ましくは10mPa・s以上、より好ましくは100mPa・s以上、さらに好ましくは1000mPa・s以上である。なお、本明細書において、(C)成分の粘度は、B形粘度計を用いて測定することができる。 The viscosity at 20 ° C. of alginic acid, CMC, and salts thereof is not particularly limited. For example, when a 1% by mass aqueous solution is used, it is preferably 1000 mPa · s from the viewpoint of solubility in water. Hereinafter, it is more preferably 500 mPa · s or less, and still more preferably 100 mPa · s or less. When measurement is impossible with a 1% by mass aqueous solution, measurement is performed as a 10% by mass aqueous solution. In that case, from the viewpoint of stability, preferably 10 mPa · s or more, more preferably 100 mPa · s or more, More preferably, it is 1000 mPa · s or more. In the present specification, the viscosity of component (C) can be measured using a B-type viscometer.
 アルギン酸、CMC、及びそれらの塩からなる群より選ばれる少なくとも1種の量は、粒子間距離の観点から、ピロリン酸第二鉄100質量部に対して、好ましくは0.5質量部以上、より好ましくは1.0質量部以上、さらに好ましくは5.0質量部以上である。また、生産効率の観点から、ピロリン酸第二鉄100質量部に対して、好ましくは300質量部以下、より好ましくは200質量部以下、さらに好ましくは100質量部以下である。なお、アルギン酸、CMC、及びそれらの塩からなる群より選ばれる少なくとも1種の量とは、用いられたアルギン酸、CMC、及びそれらの塩の合計量を意味し、成分(C)の量と記載することもある。 The amount of at least one selected from the group consisting of alginic acid, CMC, and salts thereof is preferably 0.5 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of ferric pyrophosphate from the viewpoint of the interparticle distance. 1.0 parts by mass or more, more preferably 5.0 parts by mass or more. From the viewpoint of production efficiency, the amount is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 100 parts by mass or less with respect to 100 parts by mass of ferric pyrophosphate. The amount of at least one selected from the group consisting of alginic acid, CMC, and salts thereof means the total amount of alginic acid, CMC, and salts used, and is described as the amount of component (C). Sometimes.
 レシチンとアルギン酸、CMC、及びそれらの塩からなる群より選ばれる少なくとも1種との質量割合〔成分(B)/成分(C)〕は、レシチンと多糖類の相互作用の観点から、0.001/75~5/1が好ましく、0.01/40~2/5がより好ましく、0.05/25~1/10がさらに好ましい。 The mass ratio [component (B) / component (C)] of lecithin and at least one selected from the group consisting of alginic acid, CMC, and salts thereof is 0.001 / 75 from the viewpoint of the interaction between lecithin and polysaccharide. To 5/1 is preferable, 0.01 / 40 to 2/5 is more preferable, and 0.05 / 25 to 1/10 is more preferable.
 また、本発明の鉄含有粉末組成物における成分(C)の含有量は、二次凝集抑制の観点から、好ましくは0.5質量%以上、より好ましくは1.0質量%以上、さらに好ましくは3.0質量%以上であり、粉末鉄製剤の溶解性の観点から、好ましくは75質量%以下、より好ましくは60質量%以下、さらに好ましくは50質量%以下である。 Further, the content of the component (C) in the iron-containing powder composition of the present invention is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 3.0% by mass or more, from the viewpoint of suppressing secondary aggregation. From the viewpoint of solubility of the powder iron preparation, it is preferably 75% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.
 本発明の鉄含有粉末組成物は、前記成分(A)~(C)を含有するが、本発明の効果を損なわない範囲内で、その他の添加剤を含有することができる。添加剤としては、ソルビタン脂肪酸エステルやショ糖脂肪酸エステル等の他の乳化剤、デキストリン等の他の賦形剤が挙げられる。これらの含有量は、公知技術に基づいて適宜設定することができる。 The iron-containing powder composition of the present invention contains the components (A) to (C), but can contain other additives within a range not impairing the effects of the present invention. Examples of the additive include other emulsifiers such as sorbitan fatty acid ester and sucrose fatty acid ester, and other excipients such as dextrin. These contents can be appropriately set based on known techniques.
 前記添加剤のなかでも、デキストリンは、水への溶解性の観点から、用いることが好ましい。デキストリンを添加する場合、本発明の鉄含有粉末組成物にデキストリンの含有量は、分散性の観点から、好ましくは1.0質量%以上、より好ましくは5.0質量%以上、さらに好ましくは10質量%以上であり、水への溶解性の観点から、好ましくは80質量%以下、より好ましくは70質量%以下、さらに好ましくは60質量%以下である。 Among the additives, dextrin is preferably used from the viewpoint of solubility in water. When dextrin is added, the content of dextrin in the iron-containing powder composition of the present invention is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, and further preferably 10% by mass or more from the viewpoint of dispersibility. From the viewpoint of solubility in water, it is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
 本発明の鉄含有粉末組成物は、前記成分(A)~(C)を含有するのであれば、その調製方法は特に限定されない。例えば、ピロリン酸第二鉄、レシチン、アルギン酸、CMC、及びそれらの塩からなる群より選ばれる少なくとも1種、ならびに必要により添加剤を均一に混合することで得られる。また、ピロリン酸第二鉄とレシチンが予め複合体を形成しているところに、アルギン酸、CMC、及びそれらの塩からなる群より選ばれる少なくとも1種、ならびに必要により添加剤を混合して調製してもよい。混合に用いる装置としては、特に限定はなく、粉末溶解機、ホモジナイザー、ホモディスパー、プロペラミキサー、攪拌機等が挙げられる。また、前記原料の混合時に水や溶媒等の媒体を用いてもよく、その場合は原料の混合後に粉末化を行う。粉末化に用いる装置としては、特に限定はなく、凍結乾燥機、スプレードライヤー、スラリードライヤー、ドラムドライヤー、熱風乾燥等が挙げられる。なお、得られた粉末はそのまま用いてもよいが、公知の方法に従って微粒子化してもよい。微粒子化に用いる装置は、前述の通りである。混合(攪拌)時間、温度、混合(攪拌)の強さ等は特に限定されるものではなく、使用する装置の種類等に応じて適宜設定されればよい。 The method for preparing the iron-containing powder composition of the present invention is not particularly limited as long as it contains the components (A) to (C). For example, it can be obtained by uniformly mixing at least one selected from the group consisting of ferric pyrophosphate, lecithin, alginic acid, CMC, and salts thereof, and if necessary. In addition, ferric pyrophosphate and lecithin form a complex in advance, and are prepared by mixing at least one selected from the group consisting of alginic acid, CMC, and salts thereof, and, if necessary, additives. May be. The apparatus used for mixing is not particularly limited, and examples thereof include a powder dissolver, a homogenizer, a homodisper, a propeller mixer, and a stirrer. Moreover, you may use media, such as water and a solvent, at the time of the said raw material mixing, In that case, it pulverizes after mixing of a raw material. The apparatus used for pulverization is not particularly limited, and examples thereof include a freeze dryer, a spray dryer, a slurry dryer, a drum dryer, and hot air drying. The obtained powder may be used as it is, or may be made into fine particles according to a known method. The apparatus used for atomization is as described above. The mixing (stirring) time, temperature, intensity of mixing (stirring) and the like are not particularly limited, and may be set as appropriate according to the type of apparatus used.
 なお、本発明の鉄含有粉末組成物において、ピロリン酸第二鉄が被覆されたかどうかの確認は、特に限定されるものではないが、例えば、得られた鉄含有粉末組成物を、鉄含量が10mg/100mLの濃度になるようイオン交換水で希釈して得られた液100mLを、100mLのネスラ-管に注いで室温で1日静置させても底部に沈殿が発生せず、分離が起こらない状態を被覆されたものと定義する事ができる。これは被覆された粒子同士が凝集せず、水中に安定分散された事によるものである。また、電子顕微鏡等を使用して被覆の有無を直接的に確認してもよい。 In the iron-containing powder composition of the present invention, confirmation of whether or not ferric pyrophosphate is coated is not particularly limited. For example, the obtained iron-containing powder composition has an iron content of Even if 100 mL of the solution obtained by diluting with ion-exchanged water to a concentration of 10 mg / 100 mL is poured into a 100 mL Nessler tube and allowed to stand at room temperature for 1 day, precipitation does not occur at the bottom and separation occurs. It can be defined that it is not covered. This is because the coated particles do not aggregate and are stably dispersed in water. Further, the presence or absence of coating may be directly confirmed using an electron microscope or the like.
 得られる鉄含有粉末組成物の平均粒子径は、特に限定されるものではないが、分散性の観点から、好ましくは0.8μm以下、より好ましくは0.5μm以下、さらに好ましくは0.2μm以下である。下限値は特に設定されないが、0.05μm以上が好ましい。また、体積中位粒子径は、分散安定性の観点から、好ましくは0.5μm以下、より好ましくは0.3μm以下、さらに好ましくは0.15μm以下である。下限値は特に設定されないが、0.01μm以上が好ましい。 The average particle size of the obtained iron-containing powder composition is not particularly limited, but is preferably 0.8 μm or less, more preferably 0.5 μm or less, and still more preferably 0.2 μm or less from the viewpoint of dispersibility. The lower limit is not particularly set, but is preferably 0.05 μm or more. Further, the volume median particle diameter is preferably 0.5 μm or less, more preferably 0.3 μm or less, and further preferably 0.15 μm or less from the viewpoint of dispersion stability. The lower limit is not particularly set, but is preferably 0.01 μm or more.
 また、本発明の鉄含有粉末組成物は、高温下での保存後にも分散安定性に優れることから、例えば、65℃に3日間保存後の平均粒子径は、好ましくは1.0μm以下、より好ましくは0.6μm以下、さらに好ましくは0.3μm以下である。下限値は特に設定されないが、0.05μm以上が好ましい。また、同様に保存した場合の体積中位粒子径は、好ましくは0.8μm以下、より好ましくは0.5μm以下、さらに好ましくは0.3μm以下である。下限値は特に設定されないが、0.01μm以上が好ましい。 Further, since the iron-containing powder composition of the present invention is excellent in dispersion stability even after storage at high temperature, for example, the average particle diameter after storage at 65 ° C. for 3 days is preferably 1.0 μm or less, more preferably Is 0.6 μm or less, more preferably 0.3 μm or less. The lower limit is not particularly set, but is preferably 0.05 μm or more. In addition, the volume-median particle diameter when stored in the same manner is preferably 0.8 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. The lower limit is not particularly set, but is preferably 0.01 μm or more.
 またさらに、本発明の鉄含有粉末組成物は、保存による状態変化が少ないことから、例えば、保存前の平均粒子径を100%とした場合、65℃に3日間保存した後の平均粒子径の変化率は、好ましくは±400%以内、より好ましくは±200%以内、さらに好ましくは±100%以内である。同様に、保存前の体積中位粒子径を100%とした場合、65℃に3日間保存した後の体積中位粒子径の変化率は、好ましくは±400%以内、より好ましくは±200%以内、さらに好ましくは±100%以内である。 Furthermore, since the iron-containing powder composition of the present invention has little change in state due to storage, for example, when the average particle size before storage is 100%, the average particle size after storage at 65 ° C. for 3 days The rate of change is preferably within ± 400%, more preferably within ± 200%, and even more preferably within ± 100%. Similarly, when the volume-median particle diameter before storage is 100%, the rate of change of the volume-median particle diameter after storage at 65 ° C. for 3 days is preferably within ± 400%, more preferably ± 200%. Within 100%, more preferably within ± 100%.
 かくして、本発明の鉄含有粉末組成物が得られる。 Thus, the iron-containing powder composition of the present invention is obtained.
 本発明の鉄含有組成物は粉末状であり、該組成物を体内に摂取することができるのであればその使用方法は特に限定されない。鉄分の補給あるいは維持のために用いることができ、例えば、鉄欠乏性貧血症、スポーツ貧血等に好適に用いられる。 The iron-containing composition of the present invention is in a powder form, and its use is not particularly limited as long as the composition can be taken into the body. It can be used for replenishment or maintenance of iron. For example, it is preferably used for iron deficiency anemia, sports anemia, and the like.
 本発明の鉄含有粉末組成物の使用量は、その使用方法、使用目的及び該組成物の使用対象者の年齢、体重、症状によって適宜設定され一定ではないが、例えば、鉄の量が7.5mg以上/日となる量が好ましい摂取量として挙げられる。所望の使用量範囲内において、1日内において単回で又は複数回で使用してもよく、使用時間も期間も任意である。 The amount of the iron-containing powder composition of the present invention is appropriately set according to the method of use, the purpose of use and the age, weight, and symptom of the user of the composition, but for example, the amount of iron is 7.5 mg. The amount of daily intake is the preferred intake. Within a desired use amount range, it may be used once or multiple times within a day, and the use time and period are arbitrary.
 本発明の鉄含有粉末組成物の使用対象者としては、好ましくは鉄分の補給あるいは維持を必要とするヒトであるが、ウシ、ウマ、ヤギ等の家畜動物、イヌ、ネコ、ウサギ等のペット動物、又は、マウス、ラット、モルモット、サル等の実験動物であってもよい。また、使用対象者として、鉄分が欠乏している個体だけでなく、血中の鉄分量は低くはないが、その低下が気になる個体、血中の鉄分量の低下を予防することを望む個体も含まれる。 The subject of the iron-containing powder composition of the present invention is preferably a human who needs supplementation or maintenance of iron content, but domestic animals such as cattle, horses and goats, and pet animals such as dogs, cats and rabbits. Or laboratory animals, such as a mouse | mouth, a rat, a guinea pig, and a monkey, may be sufficient. In addition, not only individuals who are deficient in iron but also individuals who are not deficient in iron, but who want to prevent a decrease in iron in their blood Individuals are also included.
 本発明の鉄含有粉末組成物は、長期保存安定性に優れることから、長期保存後においても不快な味や風味を呈することなく製品中で良好に分散するために、例えば、飲食品、医薬組成物又はこれらの原料として好適に用いられる。 Since the iron-containing powder composition of the present invention is excellent in long-term storage stability, it can be satisfactorily dispersed in the product without exhibiting an unpleasant taste or flavor even after long-term storage. It is suitably used as a product or a raw material thereof.
 飲食品としては、本発明の鉄含有粉末組成物を含有すれば特に限定はなく、例えば、鉄分を補給あるいは維持するための飲食品が挙げられる。具体的には、特定保健用食品、栄養機能食品、老人用食品、特別用途食品、機能性食品、健康補助食品(サプリメント)として、例えば、鉄分を補給あるいは維持するために用いられるものである旨の表示を付して提供することが可能になると考えられる。 The food and drink are not particularly limited as long as the iron-containing powder composition of the present invention is contained, and examples thereof include food and drink for supplying or maintaining iron. Specifically, foods for specified health use, functional nutritional foods, foods for the elderly, special-purpose foods, functional foods, health supplements (supplements), for example, to be used to supplement or maintain iron It will be possible to provide it with the display.
 かかる飲食品としては、例えば、即席麺、カップ麺、レトルト・調理食品、調理缶詰、電子レンジ食品、即席スープ・シチュー、即席みそ汁・吸い物、スープ缶詰、フリーズドライ食品等の即席食品、炭酸飲料、天然果汁、果汁飲料、清涼飲料水(果汁入りも含む)、果肉飲料、果粒入り果実食品、野菜系飲料、豆乳・豆乳飲料、コーヒー飲料、お茶飲料、粉末飲料、濃縮飲料、スポーツ飲料、栄養飲料、アルコール飲料等の嗜好飲料類、パン、マカロニ・スパゲッティ、麺類、ケーキミックス、から揚げ粉・パン粉、ギョーザ・春巻の皮等の小麦粉食品、キャラメル・キャンディー、チューイングガム、チョコレート、クッキー・ビスケット、ケーキ・パイ、スナック・クラッカー、和菓子・米菓子・豆菓子・焼菓子、ゼリー、プリン、ババロア、デザート菓子等の菓子類、しょうゆ、みそ、ソース類、トマト加工調味料、みりん類、食酢類、甘味料、魚醤、ニョクマム等の基礎調味料、風味調味料、調理ミックス、カレーの素、たれ類、ドレッシング、麺つゆ、スパイス等の複合調味料、バター、マーガリン、マヨネーズ等の油脂食品、牛乳・加工乳、乳飲料、ヨーグルト類、発酵乳飲料、乳酸菌飲料、チーズ、アイスクリーム、調製粉乳、乳児用調製粉乳、クリーム等の乳・乳製品、液卵、粉末卵、錦糸玉子等の卵加工食品、半調理冷凍食品、調理済冷凍食品等の冷凍食品、水産缶詰・ペースト類、魚肉ハム・ソーセージ、水産練り製品、水産珍味類、水産乾物類、佃煮等の水産加工品、畜産缶詰・ペースト類、畜肉ハム・ソーセージ、畜産珍味類等の畜産加工品、農産缶詰、果実缶詰、フルーツソース、フルーツプレパレーション、ジャム・マーマレード類、漬物、煮豆、農産乾物類、シリアル等の農産加工品、流動食、ベビーフード、離乳食、ふりかけ、お茶漬けのり、バー食品等の栄養食品、サプリメント、丸剤、ハードカプセル剤、錠剤〔素錠、糖衣錠、口腔内速崩壊錠、咀嚼可能錠(チュアブル錠)、発泡錠、トローチ剤、フィルムコーティング錠等を含む〕等を例示できる。なお、これらは、既成の飲食品に対して本発明の鉄含有粉末組成物を調製時に添加させたものであればよく、添加時期や添加方法については特に限定されるものではない。 Examples of such foods and drinks include instant noodles, cup noodles, retort / cooked food, cooked canned food, microwave food, instant soup / stew, instant miso soup / soup, canned soup, freeze-dried food, carbonated drinks, Natural fruit juice, fruit juice drink, soft drink (including fruit juice), fruit drink, fruit food with fruit granules, vegetable drink, soy milk / soy milk drink, coffee drink, tea drink, powdered drink, concentrated drink, sports drink, nutrition Beverages, beverages such as alcoholic beverages, bread, macaroni / spaghetti, noodles, cake mix, fried flour / bread crumbs, gyoza / spring rolls and other flour foods, caramel candy, chewing gum, chocolate, cookies / biscuits, Cake pie, snack cracker, Japanese confectionery, rice confectionery, bean confectionery, baked confectionery, jelly, pudding, Confectionery such as baloa, dessert confectionery, soy sauce, miso, sauces, tomato processing seasoning, mirin, vinegar, sweetener, fish sauce, nyokumam and other basic seasonings, flavor seasoning, cooking mix, curry base Compound seasonings such as sauces, dressings, noodle soup and spices, fat and fat foods such as butter, margarine and mayonnaise, milk and processed milk, milk drinks, yogurts, fermented milk drinks, lactic acid bacteria drinks, cheese, ice cream, preparation Powdered milk, infant formula, milk and dairy products such as cream, liquid eggs, powdered eggs, egg processed foods such as broiled eggs, frozen foods such as half-cooked frozen foods, cooked frozen foods, fishery canned foods and pastes, fish meat Hams and sausages, marine products, marine delicacies, marine dried products, marinated fish products such as boiled fish, livestock canned and pasted products, livestock processed products such as livestock ham and sausage, livestock delicacy, agricultural cans , Canned fruits, fruit sauces, fruit preparations, jams and marmalades, pickles, boiled beans, dried agricultural products, cereals and other processed agricultural products, liquid foods, baby food, baby food, sprinkles, pickled vegetables, bar foods and other nutritional foods , Supplements, pills, hard capsules, tablets [including uncoated tablets, sugar-coated tablets, intraoral quick disintegrating tablets, chewable tablets (chewable tablets), effervescent tablets, troches, film-coated tablets, etc.]. In addition, these should just add the iron-containing powder composition of this invention at the time of preparation with respect to ready-made food-drinks, and it does not specifically limit about an addition time and an addition method.
 医薬組成物としては、医薬品、医薬部外品等として幅広く利用することができる。例えば、鉄分の補給あるいは維持が望まれている任意の疾患の治療や予防のために用いることができる。具体的には、鉄欠乏性貧血症、スポーツ貧血の治療や予防の用途に好適に用いることができる。なお、本発明の医薬組成物は、本発明の鉄含有粉末組成物と同じ作用を有する他の成分等を共に配合して調製することもできる。 As a pharmaceutical composition, it can be widely used as a medicine, a quasi-drug, and the like. For example, it can be used for the treatment or prevention of any disease for which supplementation or maintenance of iron is desired. Specifically, it can be suitably used for the treatment and prevention of iron deficiency anemia and sports anemia. In addition, the pharmaceutical composition of the present invention can be prepared by blending together other components having the same action as the iron-containing powder composition of the present invention.
 医薬組成物の製剤形態としては、本発明の鉄含有粉末組成物を含有するのであれば特に制限されず、具体的には、散剤、粉末剤、細粒剤、顆粒剤、丸剤、カプセル剤、錠剤〔素錠、糖衣錠、口腔内速崩壊錠、咀嚼可能錠(チュアブル錠)、発泡錠、トローチ剤、フィルムコーティング錠等を含む〕、ドライシロップ剤、フィルム剤、液剤〔懸濁剤、乳剤、シロップ剤、リモナーデ剤等を含む〕、ゼリー剤が例示され、製菓剤〔キャンディー(飴)、グミ剤、ヌガー剤等〕も包含される。なお、カプセル剤としては、ハードカプセル剤の他に、本発明の鉄含有粉末組成物を分散させた溶液を充填したソフトカプセル剤も含まれる。 The form of the pharmaceutical composition is not particularly limited as long as it contains the iron-containing powder composition of the present invention. Specifically, powders, powders, fine granules, granules, pills, capsules , Tablets [including uncoated tablets, sugar-coated tablets, intraoral quick disintegrating tablets, chewable tablets (chewable tablets), effervescent tablets, troches, film-coated tablets, etc.], dry syrups, films, liquids (suspensions, emulsions, Examples include syrups, limonades, etc.], jelly agents, and confectionery agents (candy, gummy, nougat agents, etc.). In addition to the hard capsule, the capsule includes a soft capsule filled with a solution in which the iron-containing powder composition of the present invention is dispersed.
 本発明の飲食品及び本発明の医薬組成物は、前記の本発明の鉄含有粉末組成物の他に製剤分野や食品分野等において通常使用される担体、基剤、及び/又は添加剤等を本発明の目的を達成する範囲内で適宜配合して調製することができる。なお、これらの飲食品及び医薬組成物における本発明の鉄含有粉末組成物の含有量は、前記した本発明の鉄含有粉末組成物の好適な使用量、例えば、鉄の量が7.5mg以上/日となる量であり、常法に従って適宜設定することができる。 In addition to the iron-containing powder composition of the present invention, the food and drink of the present invention and the pharmaceutical composition of the present invention include carriers, bases, and / or additives that are usually used in the pharmaceutical field and food field. It can be prepared by appropriately blending within the range of achieving the object of the present invention. Incidentally, the content of the iron-containing powder composition of the present invention in these food and drink products and pharmaceutical compositions is the preferred use amount of the iron-containing powder composition of the present invention described above, for example, the amount of iron is 7.5 mg or more / It is the amount that makes up a day, and can be appropriately set according to a conventional method.
 以下に、実施例により本発明を具体的に説明するが、本発明はこれら実施例によってなんら限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.
〔粒径分布〕
 粒径分布はレーザー回折粒度分布測定装置(BECKMAN COULTER社製、商品名:LS 13 320)によって測定し、平均粒子径及び体積中位粒子径を求める。
[Particle size distribution]
The particle size distribution is measured with a laser diffraction particle size distribution analyzer (trade name: LS 13 320, manufactured by BECKMAN COULTER), and the average particle size and the volume median particle size are determined.
〔粘度〕
 試料を水に溶解させた1又は10質量%水溶液を調製し、20℃で30分間保持した後、下記の条件で粘度を測定する(1質量%での測定が不能な場合は、10質量%での測定を行う)。
<測粘度測定条件>
測粘測定装置:ブルックフィールド型粘度計BLII
測定温度:20℃
〔viscosity〕
Prepare a 1 or 10% by weight aqueous solution in which the sample is dissolved in water, hold it at 20 ° C for 30 minutes, and then measure the viscosity under the following conditions (if measurement at 1% by weight is impossible, 10% by weight To make measurements).
<Viscometric measurement conditions>
Viscometer: Brookfield viscometer BLII
Measurement temperature: 20 ℃
実施例1~7及び比較例1~11
 塩化第二鉄6水和物13kgをイオン交換水45kgに溶解して鉄溶液を調製した。次に、ピロリン酸四ナトリウム(10水和物)16.5kgをイオン交換水105kgに溶解したピロリン酸溶液中に、攪拌下で前記で得られた鉄溶液を徐々に添加した。中和反応によるピロリン酸第二鉄の造塩が終了した後、遠心分離(3000×g、10分間)によって上清を除去し、得られた沈殿物にイオン交換水を加えて攪拌し、再び遠心分離(3000×g、10分間)によって沈殿物を洗浄した。上清除去後、再度イオン交換水を加えて攪拌洗浄し、遠心分離(3000×g、10分間)し、3質量%のピロリン酸第二鉄となるように得られた沈殿にイオン交換水を添加した。ホモミキサーで攪拌しピロリン酸第二鉄スラリーを得た(ピロリン酸第二鉄の平均粒子径0.237μm、体積中位粒子径0.191μm)。
Examples 1 to 7 and Comparative Examples 1 to 11
An iron solution was prepared by dissolving 13 kg of ferric chloride hexahydrate in 45 kg of ion exchange water. Next, the iron solution obtained above was gradually added to a pyrophosphoric acid solution obtained by dissolving 16.5 kg of tetrasodium pyrophosphate (decahydrate) in 105 kg of ion-exchanged water. After the ferric pyrophosphate salt formation by the neutralization reaction is completed, the supernatant is removed by centrifugation (3000 × g, 10 minutes), ion-exchanged water is added to the resulting precipitate, and the mixture is stirred again. The precipitate was washed by centrifugation (3000 × g, 10 minutes). After removing the supernatant, add ion-exchanged water again, wash with stirring, centrifuge (3000 xg, 10 minutes), and add ion-exchanged water to the precipitate obtained to give 3 mass% ferric pyrophosphate. Added. The mixture was stirred with a homomixer to obtain a ferric pyrophosphate slurry (average particle size of ferric pyrophosphate 0.237 μm, volume median particle size 0.191 μm).
 前記のスラリー生成物100gに、レシチン又は酵素分解レシチン0.015g、表1又は2に示す多糖類2.1g、デキストリンを添加する場合は4.65gをそれぞれ添加し、ヒスコトロンで均質化させた後、凍結乾燥品を乳鉢ですり潰して粉末組成物を調製した。ここで、ピロリン酸第二鉄100質量部に対するレシチン/酵素分解レシチンの量は0.50質量部、ピロリン酸第二鉄100質量部に対する多糖類の量は70質量部であり、乳化剤と多糖類の質量比(乳化剤/多糖類)は0.5/70であった。また、デキストリンの量はピロリン酸第二鉄100質量部に対して155質量部であった。なお、レシチンは商品名「ADLEC RL」(ADM社製)を、酵素分解レシチンは商品名「サンレシチンL」(太陽化学社製)を、アルギン酸ソーダは商品名「キミカアルギン」(キミカ社製、20℃における1質量%の粘度30mPa・s、以降、アルギン酸ソーダAと記載する)、商品名「キミカアルギン」(キミカ社製、20℃における1質量%の粘度300mPa・s、以降、アルギン酸ソーダBと記載する)、商品名「キミカアルギン」(キミカ社製、20℃における1質量%の粘度600mPa・s、以降、アルギン酸ソーダCと記載する)、及び商品名「キミカアルギン」(キミカ社製、20℃における10質量%の粘度40mPa・s、以降、アルギン酸ソーダDと記載する)を、カルボキシメチルセルロースナトリウムは商品名「セロゲン」(第一工業製薬社製、20℃における1質量%の粘度40mPa・s)を用いた。 To 100 g of the above slurry product, 0.015 g of lecithin or enzymatically decomposed lecithin, 2.1 g of polysaccharide shown in Table 1 or 2, and 4.65 g of dextrin are added, homogenized with Hiscotron, and then lyophilized. The product was ground in a mortar to prepare a powder composition. Here, the amount of lecithin / enzymatically decomposed lecithin with respect to 100 parts by mass of ferric pyrophosphate is 0.50 parts by mass, the amount of polysaccharide with respect to 100 parts by mass of ferric pyrophosphate is 70 parts by mass, and the mass of emulsifier and polysaccharide The ratio (emulsifier / polysaccharide) was 0.5 / 70. The amount of dextrin was 155 parts by mass with respect to 100 parts by mass of ferric pyrophosphate. Lecithin is trade name “ADLEC RL” (manufactured by ADM), enzyme-degraded lecithin is trade name “Sun lecithin L” (manufactured by Taiyo Kagaku), and sodium alginate is trade name “Kimika Argin” (manufactured by Kimika Corporation, 20 Viscosity of 1% by mass at 30 ° C., 30 mPa · s, hereinafter referred to as sodium alginate A), trade name “Kimika Algin” (manufactured by Kimika, 1 mass% of viscosity at 20 ° C., 300 mPa · s, hereinafter referred to as sodium alginate) ), Trade name “Kimika Argin” (Kimika Corp., 1 mass% viscosity at 20 ° C. 600 mPa · s, hereinafter referred to as sodium alginate C), and trade name “Kimika Argin” (Kimika Corp., 10 ° C. at 10 ° C. Viscosity of 40 mPa · s in mass%, hereinafter referred to as sodium alginate D), sodium carboxymethylcellulose is trade name “Serogen” (Daiichi Kogyo Seiyaku Co., Ltd., 1 mass% viscosity of 40 mPa at 20 ° C.) s) was used.
試験例1
 得られた粉末組成物について、アルミラミネート袋に密封したものを65℃の恒温室に保存し、経時的にサンプリングを行って、その平均粒子径及び体積中位粒子径を測定した。結果を表1及び2に示す。なお、測定時点の平均粒子径及び体積中位粒子径が1μmを超えた組成については、以降のサンプリングは行わず、表中では「---」で示した。
Test example 1
The obtained powder composition, which was sealed in an aluminum laminate bag, was stored in a constant temperature room at 65 ° C., sampled over time, and the average particle size and volume median particle size were measured. The results are shown in Tables 1 and 2. In addition, for the composition whose average particle size and volume median particle size at the time of measurement exceeded 1 μm, the subsequent sampling was not performed, and it was indicated by “---” in the table.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表2より、比較例1~2は多糖類が含まれていないため、調製時にピロリン酸第二鉄の二次粒子の凝集を抑えることができなかった。比較例3はレシチンが含まれていないため、ピロリン酸第二鉄とアルギン酸ソーダの相互作用が弱く、粉末時の凝集は抑えているが、長期的には再分散性を維持できないものであった。 From Table 2, since Comparative Examples 1 and 2 did not contain polysaccharides, aggregation of secondary particles of ferric pyrophosphate could not be suppressed during preparation. Since Comparative Example 3 did not contain lecithin, the interaction between ferric pyrophosphate and sodium alginate was weak and aggregation during powder was suppressed, but redispersibility could not be maintained in the long term. .
 比較例8~11で使用している多糖類では調製時の乾燥による二次凝集が抑えられず、水溶液に再分散させても即座に沈降してしまう結果となった。また、比較例6~7は調製時の乾燥による二次凝集は抑制するが、高温保存の熱エネルギーによって分子内の触媒作用が大きくなり、多糖類主鎖、側鎖の分解が進み、保存粉末での二次凝集を抑制できなかった。比較例4~5も比較例6~7と同様に熱エネルギーにより多糖類主鎖、側鎖の分解が進み粉末での二次凝集を抑制できなかった。 In the polysaccharides used in Comparative Examples 8 to 11, secondary agglomeration due to drying at the time of preparation was not suppressed, and even when re-dispersed in an aqueous solution, it immediately settled. In Comparative Examples 6 to 7, secondary aggregation due to drying during preparation is suppressed, but the catalysis in the molecule is increased by the thermal energy of high-temperature storage, and the polysaccharide main chain and side chains are decomposed, so that the storage powder Secondary aggregation could not be suppressed. In Comparative Examples 4 to 5, as in Comparative Examples 6 to 7, decomposition of the polysaccharide main chain and side chains progressed due to thermal energy, and secondary aggregation in the powder could not be suppressed.
 一方、表1より、実施例1~7は多糖類の主鎖が分解されにくく、過度の熱に対しても二次凝集を起こしにくく、粉末状態での長期安定性に優れることが示唆される。また、粘度の異なるアルギン酸ソーダを用いた実施例2~5は、保存後の粒子径に大差は認められなかった。デキストリンの有無によっては粒子径には若干の違いが見られたが、本質的な違いはなかった。 On the other hand, Table 1 suggests that in Examples 1 to 7, the main chain of the polysaccharide is difficult to be decomposed, secondary aggregation is hardly caused even by excessive heat, and excellent long-term stability in a powder state. . In Examples 2 to 5 using sodium alginate having different viscosities, no large difference was observed in the particle diameter after storage. Although there was a slight difference in the particle size depending on the presence or absence of dextrin, there was no essential difference.
試験例2
 実施例1~7の65℃、3日間保存したサンプルについて、鉄含量が10mg/100mLの濃度になるようイオン交換水で希釈して得られた液100mLを、100mLのネスラ-管に注いで室温で静置した。
Test example 2
For the samples stored at 65 ° C. for 3 days in Examples 1 to 7, 100 mL of a solution obtained by diluting with iron-exchanged water so that the iron content was 10 mg / 100 mL was poured into a 100 mL Nessler tube at room temperature. Left at rest.
 1日後に状態を目視で確認したところ、いずれのサンプルも底部に沈殿は発生せず、分離も認められず、良好な分散性を示すことが分かった。なお、実施例4(アルギン酸ソーダCを用いた例)は一旦溶解又は分散すると良好な分散性を示すが、粉末の溶解性が若干悪く、溶解させるのに時間を要するものであった。 When the state was visually confirmed after 1 day, it was found that no precipitation occurred at the bottom of any sample, no separation was observed, and good dispersibility was exhibited. In addition, although Example 4 (example using sodium alginate C) showed good dispersibility once dissolved or dispersed, the solubility of the powder was somewhat poor, and it took time to dissolve.
試験例3
 実施例1を参照して調製したピロリン酸第二鉄200gをイオン交換水1800gに混合、分散させ、本分散液を湿式粉砕機ダイノミルによって湿式粉砕を行い、ピロリン酸第二鉄の粉砕物を10質量%含む、ピロリン酸第二鉄スラリーを得た(ピロリン酸第二鉄の平均粒子径0.268μm、体積中位粒子径0.197μm)。前記のスラリー生成物30gに、レシチン0.0105g、アルギン酸ソーダA2.55g、及びデキストリン4.2gを添加し、ヒスコトロンで均質化させた後、スプレードライにて、実施例8の粉末組成物を調製した。ピロリン酸第二鉄100質量部に対する、レシチンの量は0.35質量部、アルギン酸ソーダの量は85質量部であり、乳化剤と多糖類の質量比(乳化剤/多糖類)は0.1/24であった。また、デキストリンの量はピロリン酸第二鉄100質量部に対して140質量部であった。
Test example 3
200 g of ferric pyrophosphate prepared with reference to Example 1 was mixed and dispersed in 1800 g of ion-exchanged water, and this dispersion was wet pulverized by a wet pulverizer Dynomill. A ferric pyrophosphate slurry containing 5% by mass was obtained (average particle size of ferric pyrophosphate 0.268 μm, volume median particle size 0.197 μm). A powder composition of Example 8 was prepared by spray drying after adding 0.0105 g of lecithin, 2.55 g of sodium alginate A, and 4.2 g of dextrin to 30 g of the slurry product. The amount of lecithin relative to 100 parts by mass of ferric pyrophosphate was 0.35 parts by mass, the amount of sodium alginate was 85 parts by mass, and the mass ratio of emulsifier to polysaccharide (emulsifier / polysaccharide) was 0.1 / 24. The amount of dextrin was 140 parts by mass with respect to 100 parts by mass of ferric pyrophosphate.
 得られた粉末組成物について、アルミラミネート袋に密封したものを表3に示す温度の恒温室に保存し、経時的にサンプリングを行って平均粒子径及び体積中位粒子径を測定して、保存開始時の値を100%とした際の相対粒子径(%)をそれぞれ算出した。結果を表3に示す。なお、測定時点の相対粒子径(%)が1000%を超えた組成については、以降のサンプリングは行わず、表中では「---」で示した。 About the obtained powder composition, what was sealed in an aluminum laminate bag was stored in a temperature-controlled room at the temperature shown in Table 3, and the average particle size and volume median particle size were measured by sampling over time, and stored. The relative particle diameter (%) was calculated when the starting value was 100%. The results are shown in Table 3. In addition, about the composition whose relative particle diameter (%) at the time of a measurement exceeded 1000%, subsequent sampling was not performed but it showed with "---" in the table | surface.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表2ではアルギン酸以外の多糖類を用いた比較例4~11、レシチンを添加していない比較例3は65℃で6日間の保管で二次凝集を生じていたのに対し、表3よりアルギン酸とレシチンを併用することで65℃で1ヶ月間、55℃で2ヶ月間、42℃、37℃、25℃に至っては12ヶ月経過しても粒子径の変化率が±100%以内であった。 In Table 2, Comparative Examples 4 to 11 using polysaccharides other than alginic acid and Comparative Example 3 to which no lecithin was added produced secondary agglomeration after storage at 65 ° C. for 6 days. In combination with lecithin, the change rate of the particle size was within ± 100% even after 12 months from 65 ° C for 1 month, 55 ° C for 2 months, 42 ° C, 37 ° C and 25 ° C. It was.
試験例4
 ピロリン酸第二鉄100質量部に対するレシチン、アルギン酸ソーダA、及びデキストリンの質量比が表4に示す量となるよう使用量を変更する以外は、実施例6の粉末組成物と同様にして、実施例9~10の粉末組成物を調製した。
Test example 4
Implementation was carried out in the same manner as the powder composition of Example 6 except that the amount used was changed so that the mass ratio of lecithin, sodium alginate A, and dextrin to 100 parts by mass of ferric pyrophosphate was the amount shown in Table 4. The powder compositions of Examples 9-10 were prepared.
 実施例1、2、8~10の粉末組成物について、アルミラミネート袋に密封したものを65℃の恒温室に保存し、経時的にサンプリングを行って平均粒子径及び体積中位粒子径を測定して、保存開始時の値を100%とした際の相対粒子径(%)をそれぞれ算出した。結果を表4に示す。なお、測定時点の相対粒子径(%)が500%を超えた組成については、以降のサンプリングは行わず、表中では「---」で示した。 About the powder compositions of Examples 1, 2, and 8 to 10, those sealed in an aluminum laminate bag were stored in a constant temperature room at 65 ° C., and the average particle size and volume-median particle size were measured by sampling over time. Then, the relative particle size (%) was calculated when the value at the start of storage was taken as 100%. The results are shown in Table 4. In addition, about the composition whose relative particle diameter (%) at the time of a measurement exceeded 500%, subsequent sampling was not performed but it showed by "---" in the table | surface.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表4より、実施例1、2、8では65℃で1ヶ月の保管でも粒子径の変化率が±100%以内である。一方で、実施例9ではレシチンの割合が少ない為、分散性・安定性が若干悪くなっているが、65℃保管でも一定期間は分散性を維持している。また、実施例10ではアルギン酸の割合が少ない為、安定性が若干悪くなっているが、65℃保管でも一定期間は分散性を維持している。 From Table 4, in Examples 1, 2 and 8, the change rate of the particle diameter is within ± 100% even after storage at 65 ° C. for 1 month. On the other hand, in Example 9, since the ratio of lecithin is small, dispersibility and stability are slightly deteriorated, but the dispersibility is maintained for a certain period even when stored at 65 ° C. Moreover, in Example 10, since the ratio of alginic acid is small, the stability is slightly deteriorated, but the dispersibility is maintained for a certain period even when stored at 65 ° C.
 以下、本発明の鉄含有粉末組成物を配合した飲食品又は医薬組成物の具体的処方を例示する。これらは公知の方法に従って調製することができる。 Hereinafter, specific prescriptions of food / beverage products or pharmaceutical compositions containing the iron-containing powder composition of the present invention will be exemplified. These can be prepared according to known methods.
○鉄強化清涼飲料
 イオン交換水750mLに果糖ブドウ糖液糖100g、クエン酸2.0g、クエン酸ナトリウム0.5g、実施例1で得られた鉄含有粉末組成物0.75g、香料適量、及び着色料適量を添加し、混合後、イオン交換水を添加して1000mLに調整した後、100mLずつ瓶に詰め、90℃で10分間加熱殺菌を行い、鉄強化清涼飲料を調製する。
○ Iron-enhanced soft drink 750 mL of ion-exchange water, 100 g of fructose glucose liquid sugar, 2.0 g of citric acid, 0.5 g of sodium citrate, 0.75 g of the iron-containing powder composition obtained in Example 1, an appropriate amount of flavor, and an appropriate amount of colorant After adding and mixing, ion-exchanged water is added to adjust to 1000 mL, and then 100 mL is filled into bottles and sterilized by heating at 90 ° C. for 10 minutes to prepare an iron-reinforced soft drink.
○鉄強化乳飲料
 本発明の鉄含有粉末組成物0.2gをイオン交換水882mLに溶解させ、脱脂粉乳89.2gを添加してホモミキサーで均質化する。その後、生クリーム28.6gを加え、混合後、イオン交換水を添加して1000mLに調整した後、200mLずつ瓶に詰め、63℃、30分の殺菌処理をして、鉄強化乳飲料を得る。
Iron-enriched milk beverage 0.2 g of the iron-containing powder composition of the present invention is dissolved in 882 mL of ion-exchanged water, 89.2 g of skim milk powder is added, and homogenized with a homomixer. Thereafter, 28.6 g of fresh cream is added, and after mixing, ion-exchanged water is added to adjust to 1000 mL, and then 200 mL each is packed in a bottle and sterilized at 63 ° C. for 30 minutes to obtain an iron-enriched milk beverage.
 本発明の鉄含有粉末組成物は、長期間保存後でも安定に分散させることができることから、味、色、物性等に実質的に影響のない、鉄分補給剤として飲食品や医薬品に好適に使用することができる。 Since the iron-containing powder composition of the present invention can be stably dispersed even after long-term storage, it is suitably used for foods and drinks and pharmaceuticals as an iron supplement, having substantially no influence on taste, color, physical properties, etc. can do.

Claims (4)

  1.  (A)ピロリン酸第二鉄、(B)レシチン、ならびに(C)アルギン酸、カルボキシメチルセルロース、及びそれらの塩からなる群より選ばれる少なくとも1種を含有してなる鉄含有粉末組成物。 An iron-containing powder composition comprising (A) ferric pyrophosphate, (B) lecithin, and (C) at least one selected from the group consisting of alginic acid, carboxymethylcellulose, and salts thereof.
  2.  鉄含有粉末組成物の体積中位粒子径が0.01~0.5μmである、請求項1記載の組成物。 The composition according to claim 1, wherein the iron-containing powder composition has a volume-median particle size of 0.01 to 0.5 µm.
  3.  請求項1又は2記載の鉄含有粉末組成物を含有してなる飲食品。 Food / beverage products containing the iron-containing powder composition of Claim 1 or 2.
  4.  請求項1又は2記載の鉄含有粉末組成物を含有してなる医薬組成物。 A pharmaceutical composition comprising the iron-containing powder composition according to claim 1 or 2.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007009536A1 (en) * 2005-07-15 2007-01-25 Unilever N.V. Iron fortified food product and additive
WO2013141139A1 (en) * 2012-03-21 2013-09-26 株式会社ヤクルト本社 Iron pyrophosphate composition
WO2014038351A1 (en) * 2012-09-06 2014-03-13 株式会社ヤクルト本社 Iron- and tocopherol-fortified fermented milk product
JP5757493B1 (en) * 2014-09-24 2015-07-29 富田製薬株式会社 Solid composition for oral iron supplementation and method for producing the same
JP2015523409A (en) * 2012-07-31 2015-08-13 アレスコ・ソチエタ・ア・レスポンサビリタ・リミタータAlesco s.r.l. Solid composition containing iron for use in iron deficiency conditions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007009536A1 (en) * 2005-07-15 2007-01-25 Unilever N.V. Iron fortified food product and additive
WO2013141139A1 (en) * 2012-03-21 2013-09-26 株式会社ヤクルト本社 Iron pyrophosphate composition
JP2015523409A (en) * 2012-07-31 2015-08-13 アレスコ・ソチエタ・ア・レスポンサビリタ・リミタータAlesco s.r.l. Solid composition containing iron for use in iron deficiency conditions
WO2014038351A1 (en) * 2012-09-06 2014-03-13 株式会社ヤクルト本社 Iron- and tocopherol-fortified fermented milk product
JP5757493B1 (en) * 2014-09-24 2015-07-29 富田製薬株式会社 Solid composition for oral iron supplementation and method for producing the same

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