WO2015141346A1 - Aqueous calcium carbonate suspension, dried calcium carbonate composition, and calcium-fortified food - Google Patents

Aqueous calcium carbonate suspension, dried calcium carbonate composition, and calcium-fortified food Download PDF

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WO2015141346A1
WO2015141346A1 PCT/JP2015/054078 JP2015054078W WO2015141346A1 WO 2015141346 A1 WO2015141346 A1 WO 2015141346A1 JP 2015054078 W JP2015054078 W JP 2015054078W WO 2015141346 A1 WO2015141346 A1 WO 2015141346A1
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calcium carbonate
mass
aqueous
acid
suspension
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French (fr)
Japanese (ja)
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ゆかり 田中
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白石工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/10—Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/262—Cellulose; Derivatives thereof, e.g. ethers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16—Inorganic salts, minerals or trace elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • the present invention relates to an aqueous calcium carbonate suspension, a calcium carbonate dry composition, and a calcium-fortified food that can be added to foods and the like for the purpose of strengthening calcium.
  • Patent Document 1 An aqueous calcium carbonate suspension added to foods such as beverages for the purpose of calcium enrichment is known (Patent Document 1).
  • the aqueous calcium carbonate suspension proposed in Patent Document 1 contains cellulose and calcium carbonate in a weight ratio of 1/9 to 9/1, and contains a large amount of cellulose. Therefore, there is a problem that the viscosity becomes high.
  • An object of the present invention is to provide a calcium carbonate aqueous suspension excellent in dispersibility and suspension stability of calcium carbonate without using a large amount of cellulose, a calcium carbonate dry composition obtained by drying the calcium carbonate suspension, and calcium fortification To provide food.
  • the aqueous calcium carbonate suspension of the present invention contains 20 to 50% by mass of calcium carbonate, and 12 to 25 parts by mass of polyglycerol fatty acid ester as an additive with respect to 100 parts by mass of calcium carbonate. Is 0.3 to 3 parts by mass, crystalline cellulose is 0.3 to 5 parts by mass, and the total number of these additives is 15 parts by mass or more.
  • the fatty acid in the polyglycerin fatty acid ester is preferably at least one selected from the group consisting of caprylic acid, behenic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid and myristic acid.
  • the fatty acid in the organic acid monoglyceride is preferably at least one selected from the group consisting of acetic acid, lactic acid, succinic acid, citric acid and tartaric acid.
  • the HLB of the polyglycerol fatty acid ester is preferably within the range of 10-20.
  • the HLB of the organic acid monoglyceride is preferably in the range of 5-9.
  • the BET specific surface area of calcium carbonate is preferably in the range of 10 to 40 m 2 / g.
  • the calcium carbonate dry composition of the present invention is obtained by drying the calcium carbonate aqueous suspension of the present invention.
  • the calcium-enriched food of the present invention is characterized in that the calcium carbonate aqueous suspension of the present invention is added.
  • the calcium carbonate aqueous suspension is preferably added in an amount of 0.5 to 50% by mass.
  • a calcium carbonate aqueous suspension excellent in calcium carbonate dispersibility and suspension stability can be obtained without using a large amount of cellulose.
  • a calcium-enriched food excellent in calcium carbonate dispersibility and storage stability can be obtained without using a large amount of cellulose.
  • the content of calcium carbonate in the aqueous calcium carbonate suspension of the present invention is 20 to 50% by mass, preferably 25 to 40% by mass, and more preferably 30 to 35% by mass.
  • the content of calcium carbonate in the aqueous calcium carbonate suspension of the present invention is 20 to 50% by mass, preferably 25 to 40% by mass, and more preferably 30 to 35% by mass.
  • the BET specific surface area of calcium carbonate is preferably in the range of 10 to 40 m 2 / g, more preferably in the range of 15 to 25 m 2 / g, and further in the range of 20 to 25 m 2 / g. It is preferable to be within.
  • the BET specific surface area is too small, the dispersibility of the aqueous calcium carbonate suspension is deteriorated. If the BET specific surface area is too large, the viscosity tends to increase.
  • the calcium carbonate dry composition is prepared by drying, dry aggregation easily occurs.
  • calcium carbonate examples include synthetic calcium carbonate and natural calcium carbonate (heavy calcium carbonate).
  • the calcium carbonate is preferably synthetic calcium carbonate.
  • Synthetic calcium carbonate is not particularly limited.
  • Examples of the synthetic calcium carbonate include precipitated (collaged) calcium carbonate and light calcium carbonate.
  • Synthetic calcium carbonate can be produced, for example, by reacting calcium hydroxide with carbon dioxide.
  • Calcium hydroxide can be produced, for example, by reacting calcium oxide with water.
  • Calcium oxide can be produced, for example, by co-firing raw limestone with coke. In this case, since carbon dioxide gas is generated during firing, calcium carbonate can be produced by reacting this carbon dioxide gas with calcium hydroxide.
  • Natural calcium carbonate is obtained by pulverizing naturally produced calcium carbonate ore by a known method.
  • Examples of the method for pulverizing the raw calcium carbonate include a roller mill, a high-speed rotation mill (impact shear mill), a container drive medium mill (ball mill), a medium stirring mill, a planetary ball mill, and a jet mill.
  • the content of the polyglycerol fatty acid ester in the aqueous calcium carbonate suspension of the present invention is 12 to 25 parts by mass, preferably 12 to 20 parts by mass, more preferably 13 to 20 parts by mass with respect to 100 parts by mass of calcium carbonate. 17 parts by mass.
  • the dispersibility at the time of adding calcium carbonate aqueous suspension to a milk beverage may worsen.
  • the HLB of the polyglycerin fatty acid ester is preferably 10 to 20, more preferably 12 to 18, and further preferably 13 to 15. If the HLB is too low, the dispersibility of calcium carbonate in preparing an aqueous calcium carbonate suspension may deteriorate. When HLB is too high, the dispersibility of the calcium carbonate in the calcium carbonate aqueous suspension may be deteriorated.
  • the fatty acid in the polyglycerin fatty acid ester is preferably at least one selected from the group consisting of caprylic acid, behenic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid and myristic acid.
  • the content of the organic acid monoglyceride in the aqueous calcium carbonate suspension of the present invention is 0.3 to 3 parts by mass, preferably 0.7 to 2 parts by mass, more preferably 100 parts by mass of calcium carbonate. Is 1 to 1.5 parts by mass. Even if there is too little content of organic acid monoglyceride, and there is too much content, the dispersibility at the time of adding calcium carbonate aqueous suspension to a milk drink will worsen.
  • the HLB of the organic acid monoglyceride is preferably 5-9. When HLB is too low, the dispersibility of the calcium carbonate in a calcium carbonate aqueous suspension will worsen. If the HLB is too high, the dispersibility of calcium carbonate in the aqueous calcium carbonate suspension will be poor.
  • the fatty acid in the organic acid monoglyceride is preferably at least one selected from the group consisting of acetic acid, lactic acid, succinic acid, citric acid and tartaric acid.
  • the content of crystalline cellulose in the aqueous calcium carbonate suspension of the present invention is 0.3-5 parts by mass, preferably 0.5-2 parts by mass, more preferably 100 parts by mass of calcium carbonate. 1 to 1.5 parts by mass. If the content of crystalline cellulose is too small, sufficient dispersibility cannot be obtained. When there is too much content of crystalline cellulose, the viscosity of calcium carbonate aqueous suspension will become high, and productivity will fall.
  • Crystalline cellulose may be a mechanically pulverized product, a chemically pulverized product, or a preparation compounded with other chemicals.
  • the total number of the three kinds of additives is preferably 15 parts by mass or more. When there are too few total parts of an additive, the dispersibility at the time of adding calcium carbonate aqueous suspension to a milk beverage will worsen.
  • the calcium carbonate aqueous suspension of the present invention may contain cyclodextrin, saccharide, sucrose fatty acid ester, sodium hexametaphosphate, mineral, lecithin and the like as other additives.
  • the content is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of calcium carbonate.
  • the aqueous calcium carbonate suspension of the present invention is produced by various methods.
  • the aqueous calcium carbonate suspension of the present invention is obtained by adding calcium carbonate, polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives as necessary to water.
  • the aqueous calcium carbonate suspension of the present invention can be obtained by adding and mixing polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives as required to an aqueous suspension of calcium carbonate. Alternatively, it may be produced by wet milling a water suspension.
  • aqueous calcium carbonate suspension of the present invention is obtained by wet-grinding an aqueous suspension of calcium carbonate, and adding polyglycerol fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives as necessary. You may manufacture by adding and mixing.
  • aqueous suspension of calcium carbonate In preparing an aqueous suspension of calcium carbonate, known methods can be widely employed. For example, calcium carbonate is added to water and stirred. Next, the aqueous suspension of calcium carbonate is preferably subjected to a wet grinding treatment.
  • the wet grinding treatment can be performed using a conventionally known wet grinding device or wet grinding device. Examples of such wet grinding apparatus and wet crushing apparatus include a colloid mill, a bead mill, a sand mill, a ball mill, and a wet jet mill.
  • Polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose and other additives can be added to and mixed with an aqueous suspension of calcium carbonate before or after wet grinding. Their order of addition is not limited.
  • Polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose and other additives may be added simultaneously or sequentially.
  • any of several kinds of polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives may be added before the wet grinding treatment, and the rest may be added after the wet grinding treatment.
  • the calcium carbonate dry composition of the present invention can be prepared by, for example, drying and powdering the aqueous calcium carbonate suspension produced as described above. Drying and pulverization may be performed after drying, or may be performed at the same time.
  • drying and pulverization known drying devices and pulverizing devices can be widely used.
  • the polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, other additives, etc. in the aqueous calcium carbonate suspension are altered by heat during drying and the resuspension effect is lost, or due to charring It is preferable to prevent generation of off-flavors. For this reason, it is preferable to manage the drying temperature so as not to exceed 120 ° C.
  • an air dryer As the drying and pulverizing apparatus capable of such management, an air dryer is known. In the present invention, it is preferable to use an air dryer as the drying and pulverizing apparatus. Examples of such an air dryer include a spray dryer, a flash jet dryer, a micron dryer, and a slurry dryer. Moreover, the strong dispersion type
  • the calcium carbonate dry composition obtained is dried and powdered so that the residual moisture content is preferably in the range of 0.2 to 5% by weight, more preferably 0.2 to 3% by weight. Adjust the drying conditions of the gasifier.
  • the residual moisture content is adjusted to the above range, when the calcium carbonate dry composition of the present invention is made into an aqueous suspension again, resuspension becomes easy, and the calcium carbonate aqueous suspension before drying It is possible to obtain a re-water suspension having dispersibility and suspension stability almost unchanged from
  • Examples of the calcium-enriched food of the present invention include milk, processed milk, milk drink, yogurt, yogurt drink, soy milk, adjusted soy milk, soy milk drink, almond drink, rice milk drink, coconut milk drink, jelly drink, soft drink, Amazake, carbonated drink, guarana drink, sports drink, fruit juice drink, vegetable juice, powdered drink, coffee, cocoa, tea, powdered milk, cereal food, health food, marine products, processed fishery products, processed livestock products, processed agricultural products, cooked rice Processed products, miso soup, hospital food, nursing food, health supplements, confectionery, dessert, soup flour, rice cake, bread, instant noodles, udon, dried noodles, chilled noodles, seasonings, soup, curry, stew, frozen food, prepared food , Pickles, cooked rice, canned foods, salmon, etc.
  • the addition amount of the aqueous calcium carbonate suspension in the calcium-fortified food of the present invention is preferably in the range of 0.5 to 50% by mass, and more preferably in the range of 1.0 to 20% by mass. . If the amount added is too small, calcium fortification may be insufficient, and if the amount added is too large, preparation of a calcium fortified food may be difficult.
  • aqueous calcium carbonate suspension A water suspension of calcium carbonate, a polyglycerin fatty acid ester, an organic acid monoglyceride and crystalline cellulose were blended at the blending ratios shown in Tables 1 to 4, and ground using a wet bead mill. 9 and aqueous calcium carbonate suspensions of Comparative Examples 1-8 were prepared. Specifically, polyglycerin fatty acid is added to the aqueous suspension of calcium carbonate having the concentrations shown in Tables 1 to 4 so as to have the number of addition parts (parts by mass relative to 100 parts by weight of calcium carbonate) shown in Tables 1 to 4.
  • the ester, organic acid monoglyceride, and crystalline cellulose were added and mixed, and the resulting aqueous suspension was prepared by wet milling.
  • the following were used as calcium carbonate, polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and water.
  • Calcium carbonate synthetic calcium carbonate Porecal-N (manufactured by Taiyo Kagaku Kogyo Co., Ltd., BET specific surface area 18 m 2 / g)
  • Polyglycerin fatty acid ester Pentaglycerin monolaurate Sunsoft A-121E (manufactured by Taiyo Chemical Co., Ltd., HLB14)
  • Organic acid monoglyceride Succinic acid monoglyceride Poem B-30 (manufactured by Riken Vitamin Co., Ltd., HLB5.5)
  • Crystalline cellulose Powdered cellulose KC Flock W-400G (Nippon Paper Industries)
  • Water Tap water
  • Example 10 (Preparation of calcium carbonate dry composition) As Example 10, the calcium carbonate aqueous suspension of Example 1 was dried with a spray dryer (ADL311S-A, manufactured by Yamato Scientific Co., Ltd.) under the condition that the target residual moisture was 5% or less, and the calcium carbonate dry composition It was. Moreover, as Comparative Example 9, the calcium carbonate aqueous suspension of Comparative Example 5 was dried in the same manner to obtain a calcium carbonate dry composition.
  • a spray dryer ADL311S-A, manufactured by Yamato Scientific Co., Ltd.
  • an aqueous calcium carbonate suspension, water, skim milk powder and cream were mixed, emulsified with a high-pressure homogenizer, and then sterilized to prepare a milk beverage.
  • the blending ratio was 0.3 mass% calcium carbonate suspension, 87.6 mass% water, 9.5 mass% skim milk powder, and 2.6 mass% cream.
  • the dispersibility and turbidity of the obtained milk beverage were measured as follows.
  • the prepared milk drink was taken into two milk bottles (180 g), and left still in the refrigerator and stored. Seven days after standing, the milk bottle was opened, and the milk bottle was gently tilted to discard the liquid. The milk bottle was turned upside down, and photographs of the bottom of the milk bottle were taken immediately and after 5 minutes, and the state was evaluated according to the following criteria by visual observation.
  • Dispersibility is good (almost no residue at the bottom of the bottle) 2: Dispersibility is slightly good (sediment remains slightly circular at the bottom of the bottle) 3: Dispersibility is normal (precipitate remains in the bottle bottom) 4: Dispersibility is slightly poor (precipitate remains on the entire bottom of the bottle) 5: Poor dispersibility (sediment remains on the entire bottom of the bottle and hangs on the side of the bottle)
  • the aqueous calcium carbonate suspensions of Examples 1 to 9 according to the present invention have high resuspension properties, and the resuspensions have high suspension stability and are suitable as food calcium fortifiers. Excellent dispersibility in food. Furthermore, when the calcium carbonate dry composition of Example 10 according to the present invention is also made into an aqueous suspension again, resuspension is easy and dispersibility and suspension are almost the same as the calcium carbonate aqueous suspension before drying. It has stability, is suitable as a calcium fortifier for foods, has excellent dispersibility in foods, and has excellent storage stability.
  • milk drinks have been described as examples of calcium-enriched foods.
  • Applicable to other calcium-enriched foods such as seasonings, soups, curry, stews, frozen foods, prepared dishes, pickles, cooked rice, canned foods, and rice cakes It can, can be an excellent calcium-enriched food in dispersibility and storage stability of the calcium carbonate.

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Abstract

Provided are: an aqueous calcium carbonate suspension which can have excellent calcium carbonate dispersibility and suspension stability without requiring the use of a large amount of cellulose; a dried calcium carbonate composition which is produced by drying the aqueous calcium carbonate suspension; and a calcium-fortified food. A aqueous calcium carbonate suspension characterized by containing 20 to 50% by mass of calcium carbonate, and also containing, as additives, a polyglycerin fatty acid ester, an organic acid monoglyceride and crystalline cellulose in amounts of 12 to 25 parts by mass, 0.3 to 3 parts by mass and 0.3 to 5 parts by mass, respectively, relative to 100 parts by mass of calcium carbonate, wherein the total amount of the additives is 15 parts by mass or more.

Description

炭酸カルシウム水性懸濁液、炭酸カルシウム乾燥組成物及びカルシウム強化食品Calcium carbonate aqueous suspension, calcium carbonate dry composition, and calcium enriched food
　本発明は、カルシウム強化等の目的で食品等に添加することができる炭酸カルシウム水性懸濁液、炭酸カルシウム乾燥組成物及びカルシウム強化食品に関するものである。 The present invention relates to an aqueous calcium carbonate suspension, a calcium carbonate dry composition, and a calcium-fortified food that can be added to foods and the like for the purpose of strengthening calcium.
　飲料等の食品にカルシウム強化等の目的で添加する炭酸カルシウム水性懸濁液が知られている（特許文献１）。特許文献１で提案されている炭酸カルシウム水性懸濁液は、セルロースと炭酸カルシウムを、重量比で１／９～９／１となるように含有するものであり、多量のセルロースを含有しているため、粘度が高くなるという問題があった。 An aqueous calcium carbonate suspension added to foods such as beverages for the purpose of calcium enrichment is known (Patent Document 1). The aqueous calcium carbonate suspension proposed in Patent Document 1 contains cellulose and calcium carbonate in a weight ratio of 1/9 to 9/1, and contains a large amount of cellulose. Therefore, there is a problem that the viscosity becomes high.
特開平１０－５２８６３０号公報Japanese Patent Laid-Open No. 10-528630
　本発明の目的は、多量のセルロースを用いることなく、炭酸カルシウムの分散性及び懸濁安定性に優れた炭酸カルシウム水性懸濁液、それを乾燥して得られる炭酸カルシウム乾燥組成物、及びカルシウム強化食品を提供することにある。 An object of the present invention is to provide a calcium carbonate aqueous suspension excellent in dispersibility and suspension stability of calcium carbonate without using a large amount of cellulose, a calcium carbonate dry composition obtained by drying the calcium carbonate suspension, and calcium fortification To provide food.
　本発明の炭酸カルシウム水性懸濁液は、炭酸カルシウムが２０～５０質量％含まれており、炭酸カルシウム１００質量部に対して、添加剤としてポリグリセリン脂肪酸エステルが１２～２５質量部、有機酸モノグリセリドが０．３～３質量部、結晶セルロースが０．３～５質量部含まれており、かつこれらの添加剤の合計部数が１５質量部以上であることを特徴としている。 The aqueous calcium carbonate suspension of the present invention contains 20 to 50% by mass of calcium carbonate, and 12 to 25 parts by mass of polyglycerol fatty acid ester as an additive with respect to 100 parts by mass of calcium carbonate. Is 0.3 to 3 parts by mass, crystalline cellulose is 0.3 to 5 parts by mass, and the total number of these additives is 15 parts by mass or more.
　ポリグリセリン脂肪酸エステルにおける脂肪酸は、カプリル酸、べヘニン酸、ステアリン酸、ラウリン酸、オレイン酸、リシノール酸及びミリスチン酸からなる群より選ばれる少なくとも１種であることが好ましい。 The fatty acid in the polyglycerin fatty acid ester is preferably at least one selected from the group consisting of caprylic acid, behenic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid and myristic acid.
　有機酸モノグリセリドにおける脂肪酸は、酢酸、乳酸、コハク酸、クエン酸及び酒石酸からなる群より選ばれる少なくとも１種であることが好ましい。 The fatty acid in the organic acid monoglyceride is preferably at least one selected from the group consisting of acetic acid, lactic acid, succinic acid, citric acid and tartaric acid.
　ポリグリセリン脂肪酸エステルのＨＬＢは、１０～２０の範囲内であることが好ましい。 The HLB of the polyglycerol fatty acid ester is preferably within the range of 10-20.
　有機酸モノグリセリドのＨＬＢは、５～９の範囲内であることが好ましい。 The HLB of the organic acid monoglyceride is preferably in the range of 5-9.
　炭酸カルシウムのＢＥＴ比表面積は、１０～４０ｍ２／ｇの範囲内であることが好ましい。 The BET specific surface area of calcium carbonate is preferably in the range of 10 to 40 m 2 / g.
　本発明の炭酸カルシウム乾燥組成物は、上記本発明の炭酸カルシウム水性懸濁液を乾燥して得られることを特徴としている。 The calcium carbonate dry composition of the present invention is obtained by drying the calcium carbonate aqueous suspension of the present invention.
　本発明のカルシウム強化食品は、上記本発明の炭酸カルシウム水性懸濁液が添加されていることを特徴としている。 The calcium-enriched food of the present invention is characterized in that the calcium carbonate aqueous suspension of the present invention is added.
　炭酸カルシウム水性懸濁液は、０．５～５０質量％添加されていることが好ましい。 The calcium carbonate aqueous suspension is preferably added in an amount of 0.5 to 50% by mass.
　本発明によれば、多量のセルロースを用いることなく、炭酸カルシウムの分散性及び懸濁安定性に優れた炭酸カルシウム水性懸濁液とすることができる。 According to the present invention, a calcium carbonate aqueous suspension excellent in calcium carbonate dispersibility and suspension stability can be obtained without using a large amount of cellulose.
　本発明によれば、多量のセルロースを用いることなく、炭酸カルシウムの分散性及び保存安定性に優れたカルシウム強化食品とすることができる。 According to the present invention, a calcium-enriched food excellent in calcium carbonate dispersibility and storage stability can be obtained without using a large amount of cellulose.
　以下、好ましい実施形態について説明する。但し、以下の実施形態は単なる例示であり、本発明は以下の実施形態に限定されるものではない。 Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.
　（炭酸カルシウム）
　本発明の炭酸カルシウム水性懸濁液における炭酸カルシウムの含有量は、２０～５０質量％であり、好ましくは２５～４０質量％であり、さらに好ましくは３０～３５質量％である。炭酸カルシウムの含有量が少なすぎると、炭酸カルシウム水性懸濁液の分散性が悪くなる。また、生産コストが高くなる。炭酸カルシウムの含有量が多すぎると、粘度が上昇し、炭酸カルシウム水性懸濁液の調製が困難になる。 (Calcium carbonate)
The content of calcium carbonate in the aqueous calcium carbonate suspension of the present invention is 20 to 50% by mass, preferably 25 to 40% by mass, and more preferably 30 to 35% by mass. When there is too little content of calcium carbonate, the dispersibility of calcium carbonate aqueous suspension will worsen. In addition, the production cost increases. When there is too much content of calcium carbonate, a viscosity will rise and preparation of calcium carbonate aqueous suspension will become difficult.
　炭酸カルシウムのＢＥＴ比表面積は、１０～４０ｍ２／ｇの範囲内であることが好ましく、さらには１５～２５ｍ２／ｇの範囲内であることが好ましく、さらには２０～２５ｍ２／ｇの範囲内であることが好ましい。ＢＥＴ比表面積が小さすぎると、炭酸カルシウム水性懸濁液の分散性が悪くなる。ＢＥＴ比表面積が大きすぎると、粘度が上昇しやすくなる。また、乾燥して炭酸カルシウム乾燥組成物を調製する際に、乾燥凝集を起こしやすくなる。 The BET specific surface area of calcium carbonate is preferably in the range of 10 to 40 m 2 / g, more preferably in the range of 15 to 25 m 2 / g, and further in the range of 20 to 25 m 2 / g. It is preferable to be within. When the BET specific surface area is too small, the dispersibility of the aqueous calcium carbonate suspension is deteriorated. If the BET specific surface area is too large, the viscosity tends to increase. In addition, when the calcium carbonate dry composition is prepared by drying, dry aggregation easily occurs.
　炭酸カルシウムの具体例としては、合成炭酸カルシウム、天然炭酸カルシウム（重質炭酸カルシウム）などが挙げられる。炭酸カルシウムは、合成炭酸カルシウムであることが好ましい。 Specific examples of calcium carbonate include synthetic calcium carbonate and natural calcium carbonate (heavy calcium carbonate). The calcium carbonate is preferably synthetic calcium carbonate.
　合成炭酸カルシウムは、特に限定されない。合成炭酸カルシウムとしては、例えば沈降性（膠質）炭酸カルシウム、軽質炭酸カルシウムなどが挙げられる。合成炭酸カルシウムは、例えば水酸化カルシウムを炭酸ガスと反応させることによって製造することができる。水酸化カルシウムは、例えば酸化カルシウムを水と反応させることによって製造することができる。酸化カルシウムは、例えば石灰石原石をコークスなどで混焼することによって製造することができる。この場合、焼成時に炭酸ガスが発生するので、この炭酸ガスを水酸化カルシウムと反応させることによって炭酸カルシウムを製造することができる。 Synthetic calcium carbonate is not particularly limited. Examples of the synthetic calcium carbonate include precipitated (collaged) calcium carbonate and light calcium carbonate. Synthetic calcium carbonate can be produced, for example, by reacting calcium hydroxide with carbon dioxide. Calcium hydroxide can be produced, for example, by reacting calcium oxide with water. Calcium oxide can be produced, for example, by co-firing raw limestone with coke. In this case, since carbon dioxide gas is generated during firing, calcium carbonate can be produced by reacting this carbon dioxide gas with calcium hydroxide.
　天然炭酸カルシウムは、天然に産出する炭酸カルシウム原石を公知の方法で粉砕することにより得られるものである。炭酸カルシウム原石を粉砕する方法としては、ローラーミル、高速回転ミル（衝撃剪断ミル）、容器駆動媒体ミル（ボールミル）、媒体撹拌ミル、遊星ボールミル、ジェットミルなどで粉砕する方法が挙げられる。 Natural calcium carbonate is obtained by pulverizing naturally produced calcium carbonate ore by a known method. Examples of the method for pulverizing the raw calcium carbonate include a roller mill, a high-speed rotation mill (impact shear mill), a container drive medium mill (ball mill), a medium stirring mill, a planetary ball mill, and a jet mill.
　（ポリグリセリン脂肪酸エステル）
　本発明の炭酸カルシウム水性懸濁液におけるポリグリセリン脂肪酸エステルの含有量は、炭酸カルシウム１００質量部に対して１２～２５質量部であり、好ましくは１２～２０質量部であり、さらに好ましくは１３～１７質量部である。ポリグリセリン脂肪酸エステルの含有量が少なすぎると、炭酸カルシウム水性懸濁液を乳飲料に添加した場合の分散性が悪くなる場合がある。ポリグリセリン脂肪酸エステルの含有量が多すぎると、炭酸カルシウム水性懸濁液における炭酸カルシウムの分散性が悪くなり、炭酸カルシウム水性懸濁液を調製する際の作業性が低下したり、調製自体が困難になる場合がある。 (Polyglycerin fatty acid ester)
The content of the polyglycerol fatty acid ester in the aqueous calcium carbonate suspension of the present invention is 12 to 25 parts by mass, preferably 12 to 20 parts by mass, more preferably 13 to 20 parts by mass with respect to 100 parts by mass of calcium carbonate. 17 parts by mass. When there is too little content of polyglyceryl fatty acid ester, the dispersibility at the time of adding calcium carbonate aqueous suspension to a milk beverage may worsen. If the content of polyglycerin fatty acid ester is too large, the dispersibility of calcium carbonate in the aqueous calcium carbonate suspension will deteriorate, and the workability when preparing the aqueous calcium carbonate suspension will be reduced, or the preparation itself will be difficult It may become.
　ポリグリセリン脂肪酸エステルのＨＬＢは、１０～２０であることが好ましく、さらに好ましくは１２～１８であり、さらに好ましくは１３～１５である。ＨＬＢが低すぎると、炭酸カルシウム水性懸濁液を調製する際の炭酸カルシウムの分散性が悪くなる場合がある。ＨＬＢが高すぎると、炭酸カルシウム水性懸濁液における炭酸カルシウムの分散性が悪くなる場合がある。 The HLB of the polyglycerin fatty acid ester is preferably 10 to 20, more preferably 12 to 18, and further preferably 13 to 15. If the HLB is too low, the dispersibility of calcium carbonate in preparing an aqueous calcium carbonate suspension may deteriorate. When HLB is too high, the dispersibility of the calcium carbonate in the calcium carbonate aqueous suspension may be deteriorated.
　ポリグリセリン脂肪酸エステルにおける脂肪酸は、カプリル酸、べヘニン酸、ステアリン酸、ラウリン酸、オレイン酸、リシノール酸及びミリスチン酸からなる群より選ばれる少なくとも１種であることが好ましい。 The fatty acid in the polyglycerin fatty acid ester is preferably at least one selected from the group consisting of caprylic acid, behenic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid and myristic acid.
　（有機酸モノグリセリド）
　本発明の炭酸カルシウム水性懸濁液における有機酸モノグリセリドの含有量は、炭酸カルシウム１００質量部に対して０．３～３部質量であり、好ましくは０．７～２質量部であり、さらに好ましくは１～１．５質量部である。有機酸モノグリセリドの含有量が少なすぎても、含有量が多すぎても炭酸カルシウム水性懸濁液を乳飲料に添加した場合の分散性が悪くなる。有機酸モノグリセリドのＨＬＢは、５～９であることが好ましい。ＨＬＢが低すぎると、炭酸カルシウム水性懸濁液における炭酸カルシウムの分散性が悪くなる。ＨＬＢが高すぎると、炭酸カルシウム水性懸濁液における炭酸カルシウムの分散性が悪くなる。 (Organic acid monoglyceride)
The content of the organic acid monoglyceride in the aqueous calcium carbonate suspension of the present invention is 0.3 to 3 parts by mass, preferably 0.7 to 2 parts by mass, more preferably 100 parts by mass of calcium carbonate. Is 1 to 1.5 parts by mass. Even if there is too little content of organic acid monoglyceride, and there is too much content, the dispersibility at the time of adding calcium carbonate aqueous suspension to a milk drink will worsen. The HLB of the organic acid monoglyceride is preferably 5-9. When HLB is too low, the dispersibility of the calcium carbonate in a calcium carbonate aqueous suspension will worsen. If the HLB is too high, the dispersibility of calcium carbonate in the aqueous calcium carbonate suspension will be poor.
　有機酸モノグリセリドにおける脂肪酸は、酢酸、乳酸、コハク酸、クエン酸及び酒石酸からなる群より選ばれる少なくとも１種であることが好ましい。 The fatty acid in the organic acid monoglyceride is preferably at least one selected from the group consisting of acetic acid, lactic acid, succinic acid, citric acid and tartaric acid.
　（結晶セルロース）
　本発明の炭酸カルシウム水性懸濁液における結晶セルロースの含有量は、炭酸カルシウム１００質量部に対して０．３～５質量部であり、好ましくは０．５～２質量部であり、さらに好ましくは１～１．５質量部である。結晶セルロースの含有量が少なすぎると、十分な分散性を得られない。結晶セルロースの含有量が多すぎると、炭酸カルシウム水性懸濁液の粘度が高くなり、生産性が低下する。 (Crystalline cellulose)
The content of crystalline cellulose in the aqueous calcium carbonate suspension of the present invention is 0.3-5 parts by mass, preferably 0.5-2 parts by mass, more preferably 100 parts by mass of calcium carbonate. 1 to 1.5 parts by mass. If the content of crystalline cellulose is too small, sufficient dispersibility cannot be obtained. When there is too much content of crystalline cellulose, the viscosity of calcium carbonate aqueous suspension will become high, and productivity will fall.
　結晶セルロースは、機械的粉砕品、化学的粉砕品、他の薬品と複合化された製剤のいずれを用いてもよい。 Crystalline cellulose may be a mechanically pulverized product, a chemically pulverized product, or a preparation compounded with other chemicals.
　上記３種の添加剤の合計部数は１５質量部以上であることが好ましい。添加剤の合計部数が少なすぎると、炭酸カルシウム水性懸濁液を乳飲料に添加した場合の分散性が悪くなる。 The total number of the three kinds of additives is preferably 15 parts by mass or more. When there are too few total parts of an additive, the dispersibility at the time of adding calcium carbonate aqueous suspension to a milk beverage will worsen.
　（その他の添加物）
　本発明の炭酸カルシウム水性懸濁液には、その他の添加物として、サイクロデキストリン、糖類、ショ糖脂肪酸エステル、ヘキサメタリン酸ナトリム、ミネラル分、レシチン類等が含まれていてもよい。その含有量は、炭酸カルシウム１００質量部に対して０．１～５質量部の範囲内であることが好ましい。 (Other additives)
The calcium carbonate aqueous suspension of the present invention may contain cyclodextrin, saccharide, sucrose fatty acid ester, sodium hexametaphosphate, mineral, lecithin and the like as other additives. The content is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of calcium carbonate.
　（炭酸カルシウム水性懸濁液の調製方法）
　本発明の炭酸カルシウム水性懸濁液は、種々の方法により製造される。 (Method for preparing calcium carbonate aqueous suspension)
The aqueous calcium carbonate suspension of the present invention is produced by various methods.
　例えば、本発明の炭酸カルシウム水性懸濁液は、炭酸カルシウム、ポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロース、及び必要に応じてその他の添加物を水に添加し、得られた水懸濁液を湿式摩砕することにより製造することができる。 For example, the aqueous calcium carbonate suspension of the present invention is obtained by adding calcium carbonate, polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives as necessary to water. Can be produced by wet grinding.
　また、本発明の炭酸カルシウム水性懸濁液は、炭酸カルシウムの水懸濁液に、ポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロース、及び必要に応じてその他の添加物を添加混合し、得られた水懸濁液を湿式摩砕することにより製造してもよい。 The aqueous calcium carbonate suspension of the present invention can be obtained by adding and mixing polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives as required to an aqueous suspension of calcium carbonate. Alternatively, it may be produced by wet milling a water suspension.
　また、本発明の炭酸カルシウム水性懸濁液は、炭酸カルシウムの水懸濁液を湿式摩砕し、これにポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロース、及び必要に応じてその他の添加物を添加混合することにより製造してもよい。 Further, the aqueous calcium carbonate suspension of the present invention is obtained by wet-grinding an aqueous suspension of calcium carbonate, and adding polyglycerol fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives as necessary. You may manufacture by adding and mixing.
　炭酸カルシウムの水懸濁液を調製するに当たっては、公知の方法を広く採用することができる。例えば、炭酸カルシウムを水に添加し、攪拌する。次に炭酸カルシウムの水懸濁液を湿式摩砕処理することが好ましい。湿式摩砕処理は、従来公知の湿式摩砕装置や湿式破砕装置を用いて行うことができる。このような湿式摩砕装置や湿式破砕装置としては、例えばコロイドミル、ビーズミル、サンドミル、ボールミル、湿式ジェットミルなどを挙げることができる。 In preparing an aqueous suspension of calcium carbonate, known methods can be widely employed. For example, calcium carbonate is added to water and stirred. Next, the aqueous suspension of calcium carbonate is preferably subjected to a wet grinding treatment. The wet grinding treatment can be performed using a conventionally known wet grinding device or wet grinding device. Examples of such wet grinding apparatus and wet crushing apparatus include a colloid mill, a bead mill, a sand mill, a ball mill, and a wet jet mill.
　ポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロースやその他の添加物は、湿式摩砕処理の前または後に、炭酸カルシウムの水懸濁液に添加、混合することができる。それらの添加順序は限定されるものではない。 Polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose and other additives can be added to and mixed with an aqueous suspension of calcium carbonate before or after wet grinding. Their order of addition is not limited.
　ポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロースやその他の添加物は、同時に添加されてもよいし、順次添加されてもよい。 Polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose and other additives may be added simultaneously or sequentially.
　またポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロースやその他の添加物は、いずれか数種を湿式摩砕処理の前に添加し、残りを湿式摩砕処理の後に添加してもよい。 In addition, any of several kinds of polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and other additives may be added before the wet grinding treatment, and the rest may be added after the wet grinding treatment.
　（炭酸カルシウム乾燥組成物の調製方法）
　本発明の炭酸カルシウム乾燥組成物は、上記のようにして製造した炭酸カルシウム水性懸濁液を、例えば、乾燥及び粉末化することにより調製することができる。乾燥及び粉末化は、乾燥を行った後に粉末化してもよいし、乾燥及び粉末化を同時に行ってもよい。 (Method for preparing calcium carbonate dry composition)
The calcium carbonate dry composition of the present invention can be prepared by, for example, drying and powdering the aqueous calcium carbonate suspension produced as described above. Drying and pulverization may be performed after drying, or may be performed at the same time.
　乾燥及び粉末化に当たっては、公知の乾燥装置及び粉末化装置を広く使用することができる。本発明では、特に炭酸カルシウム水性懸濁液中のポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロース、その他の添加物などが乾燥時の熱により変質して再懸濁効果がなくなったり、焦げ等による異臭発生が起こらないようにすることが好ましい。このため、乾燥温度は、１２０℃を超えないように管理することが好ましい。 For drying and pulverization, known drying devices and pulverizing devices can be widely used. In the present invention, the polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, other additives, etc. in the aqueous calcium carbonate suspension are altered by heat during drying and the resuspension effect is lost, or due to charring It is preferable to prevent generation of off-flavors. For this reason, it is preferable to manage the drying temperature so as not to exceed 120 ° C.
　このような管理のできる乾燥、粉末化装置としては、気流乾燥機が知られており、本発明では乾燥、粉末化装置として気流乾燥機を使用するのが好ましい。このような気流乾燥機としては、例えばスプレードライヤー、フラッシュジェットドライヤー、ミクロンドライヤー、スラリードライヤーなどを挙げることができる。また、ドライマイスタとして市販されている強力分散型気流乾燥機を使用することもできる。 As the drying and pulverizing apparatus capable of such management, an air dryer is known. In the present invention, it is preferable to use an air dryer as the drying and pulverizing apparatus. Examples of such an air dryer include a spray dryer, a flash jet dryer, a micron dryer, and a slurry dryer. Moreover, the strong dispersion type | formula airflow dryer marketed as a dry meister can also be used.
　乾燥、粉末化に当たっては、得られる炭酸カルシウム乾燥組成物の残留水分量が、好ましくは０．２～５重量％、さらに好ましくは０．２～３重量％の範囲内になるよう、乾燥、粉末化装置の乾燥条件を調整する。残留水分量を上記範囲に調整しておくと、本発明の炭酸カルシウム乾燥組成物を再び水懸濁液とした場合、再懸濁化が容易になり、また乾燥前の炭酸カルシウム水性懸濁液と殆ど変わらない分散性、懸濁安定性を有する再水懸濁液とすることができる。 In drying and powdering, the calcium carbonate dry composition obtained is dried and powdered so that the residual moisture content is preferably in the range of 0.2 to 5% by weight, more preferably 0.2 to 3% by weight. Adjust the drying conditions of the gasifier. When the residual moisture content is adjusted to the above range, when the calcium carbonate dry composition of the present invention is made into an aqueous suspension again, resuspension becomes easy, and the calcium carbonate aqueous suspension before drying It is possible to obtain a re-water suspension having dispersibility and suspension stability almost unchanged from
　（カルシウム強化食品）
　本発明のカルシウム強化食品としては、例えば、牛乳、加工乳、乳飲料、ヨーグルト、ヨーグルト飲料、豆乳、調整豆乳、豆乳飲料、アーモンド飲料、ライスミルク飲料、ココナッツミルク飲料、ゼリー状飲料、清涼飲料、甘酒、炭酸飲料、ガラナ飲料、スポーツ飲料、果汁飲料、野菜ジュース、粉末飲料、コーヒー、ココア、茶、粉ミルク、シリアル食品、健康食品、水産練り製品、水産加工品、畜産加工品、農産加工品、米飯加工品、味噌汁、病院食、介護食、健康補助食品、菓子、デザート、お汁粉、米菓、パン、即席麺、うどん、乾麺、チルド麺、調味料、スープ、カレー、シチュー、冷凍食品、惣菜、漬物、米飯、缶詰、蒲鉾等などが挙げられる。 (Calcium-enriched food)
Examples of the calcium-enriched food of the present invention include milk, processed milk, milk drink, yogurt, yogurt drink, soy milk, adjusted soy milk, soy milk drink, almond drink, rice milk drink, coconut milk drink, jelly drink, soft drink, Amazake, carbonated drink, guarana drink, sports drink, fruit juice drink, vegetable juice, powdered drink, coffee, cocoa, tea, powdered milk, cereal food, health food, marine products, processed fishery products, processed livestock products, processed agricultural products, cooked rice Processed products, miso soup, hospital food, nursing food, health supplements, confectionery, dessert, soup flour, rice cake, bread, instant noodles, udon, dried noodles, chilled noodles, seasonings, soup, curry, stew, frozen food, prepared food , Pickles, cooked rice, canned foods, salmon, etc.
　本発明のカルシウム強化食品における炭酸カルシウム水性懸濁液の添加量は、０．５～５０質量％の範囲内であることが好ましく、１．０～２０質量％の範囲内であることがさらに好ましい。添加量が少なすぎると、カルシウム強化が不十分になる場合があり、添加量が多すぎると、カルシウム強化食品の調製が困難になる場合がある。 The addition amount of the aqueous calcium carbonate suspension in the calcium-fortified food of the present invention is preferably in the range of 0.5 to 50% by mass, and more preferably in the range of 1.0 to 20% by mass. . If the amount added is too small, calcium fortification may be insufficient, and if the amount added is too large, preparation of a calcium fortified food may be difficult.
　（炭酸カルシウム水性懸濁液の調製）
　表１～表４に示す配合割合で、炭酸カルシウムの水懸濁液、ポリグリセリン脂肪酸エステル、有機酸モノグリセリド及び結晶セルロースを配合し、湿式のビーズミルを用いて摩砕処理して、実施例１～９及び比較例１～８の炭酸カルシウム水性懸濁液を調製した。具体的には、表１～表４に示す濃度の炭酸カルシウムの水懸濁液に、表１～表４に示す添加部数（炭酸カルシウム１００重量部に対する質量部）となるように、ポリグリセリン脂肪酸エステル、有機酸モノグリセリド、及び結晶セルロースを添加混合し、得られた水懸濁液を湿式摩砕することにより製造した。炭酸カルシウム、ポリグリセリン脂肪酸エステル、有機酸モノグリセリド、結晶セルロース、及び水としては、以下のものを用いた。 (Preparation of aqueous calcium carbonate suspension)
A water suspension of calcium carbonate, a polyglycerin fatty acid ester, an organic acid monoglyceride and crystalline cellulose were blended at the blending ratios shown in Tables 1 to 4, and ground using a wet bead mill. 9 and aqueous calcium carbonate suspensions of Comparative Examples 1-8 were prepared. Specifically, polyglycerin fatty acid is added to the aqueous suspension of calcium carbonate having the concentrations shown in Tables 1 to 4 so as to have the number of addition parts (parts by mass relative to 100 parts by weight of calcium carbonate) shown in Tables 1 to 4. The ester, organic acid monoglyceride, and crystalline cellulose were added and mixed, and the resulting aqueous suspension was prepared by wet milling. The following were used as calcium carbonate, polyglycerin fatty acid ester, organic acid monoglyceride, crystalline cellulose, and water.
　・炭酸カルシウム：合成炭酸カルシウム　ポアカル－Ｎ（太陽化学工業社製、ＢＥＴ比表面積１８ｍ２／ｇ）
　・ポリグリセリン脂肪酸エステル：モノラウリン酸ペンタグリセリン　サンソフトＡ－１２１Ｅ（太陽化学工業社製、ＨＬＢ１４）
　・有機酸モノグリセリド：コハク酸モノグリセリド　ポエムＢ－３０（理研ビタミン社製、ＨＬＢ５．５）
　・結晶セルロース：粉末セルロース　ＫＣフロックＷ－４００Ｇ（日本製紙社製）
　・水：水道水 Calcium carbonate: synthetic calcium carbonate Porecal-N (manufactured by Taiyo Kagaku Kogyo Co., Ltd., BET specific surface area 18 m 2 / g)
Polyglycerin fatty acid ester: Pentaglycerin monolaurate Sunsoft A-121E (manufactured by Taiyo Chemical Co., Ltd., HLB14)
Organic acid monoglyceride: Succinic acid monoglyceride Poem B-30 (manufactured by Riken Vitamin Co., Ltd., HLB5.5)
・ Crystalline cellulose: Powdered cellulose KC Flock W-400G (Nippon Paper Industries)
・ Water: Tap water
　（炭酸カルシウム水性懸濁液のスラリー物性）
　実施例１～９及び比較例１～８の炭酸カルシウム水性懸濁液の粘度を測定した。 (Slurry properties of calcium carbonate aqueous suspension)
The viscosities of the aqueous calcium carbonate suspensions of Examples 1 to 9 and Comparative Examples 1 to 8 were measured.
　（粘度）
　２５℃に温調したスラリーのＢＭ粘度（６０ｒｐｍ）を測定した。 (viscosity)
The BM viscosity (60 rpm) of the slurry adjusted to 25 ° C. was measured.
　（炭酸カルシウム乾燥組成物の調製）
　実施例１０として、実施例１の炭酸カルシウム水性懸濁液をスプレードライヤー（ヤマト科学株式会社製　ＡＤＬ３１１Ｓ－Ａ）にて、目標の残留水分５％以下になる条件で乾燥させ、炭酸カルシウム乾燥組成物とした。また、比較例９として、比較例５の炭酸カルシウム水性懸濁液を同様にして乾燥させ、炭酸カルシウム乾燥組成物とした。 (Preparation of calcium carbonate dry composition)
As Example 10, the calcium carbonate aqueous suspension of Example 1 was dried with a spray dryer (ADL311S-A, manufactured by Yamato Scientific Co., Ltd.) under the condition that the target residual moisture was 5% or less, and the calcium carbonate dry composition It was. Moreover, as Comparative Example 9, the calcium carbonate aqueous suspension of Comparative Example 5 was dried in the same manner to obtain a calcium carbonate dry composition.
　（炭酸カルシウム水性懸濁液および炭酸カルシウム乾燥組成物の応用評価）
　実施例１～９及び比較例１～８の炭酸カルシウム水性懸濁液、あるいは、実施例１０及び比較例９の炭酸カルシウム乾燥組成物を水に加え、１０質量％の水性懸濁液としたものと、脱脂粉乳と、クリームを用いて、乳飲料を調製し、炭酸カルシウム水性懸濁液の分散性を評価した。 (Application evaluation of calcium carbonate aqueous suspension and calcium carbonate dry composition)
The calcium carbonate aqueous suspensions of Examples 1 to 9 and Comparative Examples 1 to 8 or the calcium carbonate dry compositions of Example 10 and Comparative Example 9 were added to water to form a 10% by mass aqueous suspension. And milk drink was prepared using skim milk powder and cream, and the dispersibility of calcium carbonate aqueous suspension was evaluated.
　具体的には、炭酸カルシウム水性懸濁液と水、脱脂粉乳、クリームを混合し、高圧ホモジナイザーにて乳化し、続いて殺菌を行い乳飲料を調製した。配合割合は、炭酸カルシウム水性懸濁液０．３質量％、水８７．６質量％、脱脂粉乳９．５質量％、クリーム２．６質量％とした。 Specifically, an aqueous calcium carbonate suspension, water, skim milk powder and cream were mixed, emulsified with a high-pressure homogenizer, and then sterilized to prepare a milk beverage. The blending ratio was 0.3 mass% calcium carbonate suspension, 87.6 mass% water, 9.5 mass% skim milk powder, and 2.6 mass% cream.
　得られた乳飲料について、以下のようにして、分散性、及び濁度を測定した。 The dispersibility and turbidity of the obtained milk beverage were measured as follows.
　（分散性）
　調製した乳飲料を牛乳瓶２本（１８０ｇ）に取り、冷蔵庫中で静置し、保管した。静置７日後、牛乳瓶を開封し、牛乳瓶を静かに傾けて液体分を捨てた。牛乳瓶を逆さにし、牛乳瓶の底の写真を直後及び５分後に撮影し、その状態を目視による以下の基準で評価した。 (Dispersibility)
The prepared milk drink was taken into two milk bottles (180 g), and left still in the refrigerator and stored. Seven days after standing, the milk bottle was opened, and the milk bottle was gently tilted to discard the liquid. The milk bottle was turned upside down, and photographs of the bottom of the milk bottle were taken immediately and after 5 minutes, and the state was evaluated according to the following criteria by visual observation.
　１：分散性が良い（瓶底にほとんど残らない）
　２：分散性がやや良い（瓶底に沈殿物がわずかに円状に残る）
　３：分散性が普通（瓶底に沈殿物が円状に残る）
　４：分散性がやや悪い（瓶底全面に沈殿物が残る）
　５：分散性が悪い（瓶底全面に沈殿物が残り、瓶側面にも垂れる） 1: Dispersibility is good (almost no residue at the bottom of the bottle)
2: Dispersibility is slightly good (sediment remains slightly circular at the bottom of the bottle)
3: Dispersibility is normal (precipitate remains in the bottle bottom)
4: Dispersibility is slightly poor (precipitate remains on the entire bottom of the bottle)
5: Poor dispersibility (sediment remains on the entire bottom of the bottle and hangs on the side of the bottle)
　（濁度）
　上記のようにして分散性を評価した後、牛乳瓶内の沈殿物に水を１５０ｇ添加し、濁度を測定した。濁度の測定は、デジタル濁度測定器（ＨＩ９３７０３―Ｂ型、ハンナインスツルメンツ・ジャパン社製）を用いた。 (Turbidity)
After evaluating dispersibility as described above, 150 g of water was added to the precipitate in the milk bottle, and the turbidity was measured. The turbidity was measured using a digital turbidity measuring instrument (HI93703-B type, manufactured by Hanna Instruments Japan).
　結果を、表１～表５に示す。 The results are shown in Tables 1 to 5.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　以上のように、本発明に従う実施例１～９の炭酸カルシウム水性懸濁液は再懸濁性が高く、その再懸濁液は懸濁安定性が高く、食品用カルシウム強化剤として適しており、食品中への分散性に優れている。さらに本発明に従う実施例１０の炭酸カルシウム乾燥組成物も再び水懸濁液とした場合、再懸濁化が容易であり、乾燥前の炭酸カルシウム水性懸濁液と殆ど変わらない分散性、懸濁安定性を有し、食品用カルシウム強化剤として適しており、食品中への分散性に優れ、保存安定性にも優れている。 As described above, the aqueous calcium carbonate suspensions of Examples 1 to 9 according to the present invention have high resuspension properties, and the resuspensions have high suspension stability and are suitable as food calcium fortifiers. Excellent dispersibility in food. Furthermore, when the calcium carbonate dry composition of Example 10 according to the present invention is also made into an aqueous suspension again, resuspension is easy and dispersibility and suspension are almost the same as the calcium carbonate aqueous suspension before drying. It has stability, is suitable as a calcium fortifier for foods, has excellent dispersibility in foods, and has excellent storage stability.
　上記の実施例では、カルシウム強化食品として、乳飲料を例にして説明したが、本発明はこれに限定されるものではなく、ヨーグルト、ヨーグルト飲料、豆乳、調整豆乳、豆乳飲料、アーモンド飲料、ライスミルク飲料、ココナッツミルク飲料、ゼリー状飲料、清涼飲料、甘酒、炭酸飲料、ガラナ飲料、スポーツ飲料、果汁飲料、野菜ジュース、粉末飲料、コーヒー、ココア、茶、粉ミルク、シリアル食品、健康食品、水産練り製品、水産加工品、畜産加工品、農産加工品、米飯加工品、味噌汁、病院食、介護食、健康補助食品、菓子、デザート、お汁粉、米菓、パン、即席麺、うどん、乾麺、チルド麺、調味料、スープ、カレー、シチュー、冷凍食品、惣菜、漬物、米飯、缶詰、蒲鉾等のその他のカルシウム強化食品にも、適用することができ、炭酸カルシウムの分散性及び保存安定性に優れたカルシウム強化食品にすることができる。 In the above embodiments, milk drinks have been described as examples of calcium-enriched foods. However, the present invention is not limited to this, and yogurt, yogurt drinks, soy milk, adjusted soy milk, soy milk drinks, almond drinks, rice Milk drink, coconut milk drink, jelly drink, soft drink, amazake, carbonated drink, guarana drink, sports drink, fruit juice drink, vegetable juice, powdered drink, coffee, cocoa, tea, powdered milk, cereal food, health food, marine products Processed fishery products, processed livestock products, processed agricultural products, processed rice products, miso soup, hospital food, nursing food, health supplements, confectionery, dessert, soup flour, rice cake, bread, instant noodles, udon, dried noodles, chilled noodles Applicable to other calcium-enriched foods such as seasonings, soups, curry, stews, frozen foods, prepared dishes, pickles, cooked rice, canned foods, and rice cakes It can, can be an excellent calcium-enriched food in dispersibility and storage stability of the calcium carbonate.

Claims (9)

  1. 　炭酸カルシウムが２０～５０質量％含まれており、炭酸カルシウム１００質量部に対して、添加剤としてポリグリセリン脂肪酸エステルが１２～２５質量部、有機酸モノグリセリドが０．３～３質量部、結晶セルロースが０．３～５質量部含まれており、かつこれらの添加剤の合計部数が１５質量部以上である炭酸カルシウム水性懸濁液。 20 to 50% by mass of calcium carbonate is contained, and 12 to 25 parts by mass of polyglycerol fatty acid ester, 0.3 to 3 parts by mass of organic acid monoglyceride as additives are added to 100 parts by mass of calcium carbonate, crystalline cellulose Is contained in an amount of 0.3 to 5 parts by mass, and the total number of these additives is 15 parts by mass or more.
  2. 　ポリグリセリン脂肪酸エステルにおける脂肪酸が、カプリル酸、べヘニン酸、ステアリン酸、ラウリン酸、オレイン酸、リシノール酸及びミリスチン酸からなる群より選ばれる少なくとも１種である、請求項１に記載の炭酸カルシウム水性懸濁液。 The calcium carbonate aqueous solution according to claim 1, wherein the fatty acid in the polyglycerol fatty acid ester is at least one selected from the group consisting of caprylic acid, behenic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid and myristic acid. Suspension.
  3. 　有機酸モノグリセリドにおける脂肪酸が、酢酸、乳酸、コハク酸、クエン酸及び酒石酸からなる群より選ばれる少なくとも１種である、請求項１または２に記載の炭酸カルシウム水性懸濁液。 The aqueous calcium carbonate suspension according to claim 1 or 2, wherein the fatty acid in the organic acid monoglyceride is at least one selected from the group consisting of acetic acid, lactic acid, succinic acid, citric acid and tartaric acid.
  4. 　ポリグリセリン脂肪酸エステルのＨＬＢが、１０～２０の範囲内である、請求項１～３のいずれか一項に記載の炭酸カルシウム水性懸濁液。 The aqueous calcium carbonate suspension according to any one of claims 1 to 3, wherein the HLB of the polyglycerol fatty acid ester is in the range of 10 to 20.
  5. 　有機酸モノグリセリドのＨＬＢが、５～９の範囲内である、請求項１～４のいずれか一項に記載の炭酸カルシウム水性懸濁液。 The aqueous calcium carbonate suspension according to any one of claims 1 to 4, wherein the organic acid monoglyceride has an HLB in the range of 5 to 9.
  6. 　炭酸カルシウムのＢＥＴ比表面積が、１０～４０ｍ２／ｇの範囲内である、請求項１～５のいずれか一項に記載の炭酸カルシウム水性懸濁液。 The aqueous calcium carbonate suspension according to any one of claims 1 to 5, wherein the calcium carbonate has a BET specific surface area of 10 to 40 m 2 / g.
  7. 　請求項１～６のいずれか一項に記載の炭酸カルシウム水性懸濁液を乾燥して得られる、炭酸カルシウム乾燥組成物。 A dry calcium carbonate composition obtained by drying the aqueous calcium carbonate suspension according to any one of claims 1 to 6.
  8. 　請求項１～６のいずれか一項に記載の炭酸カルシウム水性懸濁液が添加されている、カルシウム強化食品。 A calcium-fortified food to which the aqueous calcium carbonate suspension according to any one of claims 1 to 6 is added.
  9. 　前記炭酸カルシウム水性懸濁液が、０．５～５０質量％添加されている、請求項８に記載のカルシウム強化食品。 The calcium-fortified food according to claim 8, wherein 0.5 to 50% by mass of the calcium carbonate aqueous suspension is added.
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