JP2001299280A - Calcium supplement including polysaccharide having carboxyl group and calcium-enriched agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a calcium supplement that comprises a complex of polysaccharides having carboxyl groups and calcium compounds in which the fine particles having nanometer order of the calcium compound slightly soluble in water and are stably dispersed in no particle separation, coagulation and the like, and having adverse effect on a smoothness and a taste. SOLUTION: The objective calcium supplement characteristically comprises a polysaccharide/calcium compound complex including a polysaccharide bearing carboxyl groups in the molecule and fine particles of a calcium compound that has a particle size of <=500 nm and is slightly soluble in water at a weight ratio of 10/90-99.9/0.1. In another embodiment, the calcium compound slightly soluble in water is synthesized in the presence of the polysaccharide bearing carboxyl groups, whereby the dispersion stability is largely improved. This stabilized dispersion is used to the objective calcium supplement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calcium reinforcing agent in which a poorly water-soluble calcium compound is dispersed in fine particles in which the dispersion stability in water is improved by using a polysaccharide containing a carboxyl group in the molecule. And its manufacturing method. Further, the present invention relates to a calcium reinforcing agent comprising a citric acid / calcium compound composite having excellent dispersion stability, which is characterized by synthesizing a calcium compound hardly soluble in water in the presence of citric acid, and a method for producing the same.

[0002]

2. Description of the Related Art It is said that the amount of calcium required by Japanese people per day is 600 mg. However, according to the National Nutrition Survey conducted by the Ministry of Health and Welfare, calcium intake has been Never met. It is pointed out that the reasons for this are regional background of low calcium in Japanese soil, differences in food culture, and changes in dietary habits. There is no problem if you consciously consume foods rich in calcium to get the required amount of calcium, but the essence of this problem is that you cannot do it.

[0003] In order to solve this problem, there is a method in which calcium is added to a food containing almost no calcium so that calcium which tends to be insufficient can be supplied. In this method, various calcium agents derived from natural products or artificially synthesized are known. Natural materials include eggshells, shells, and animal bones.Since these natural materials are basically insoluble in water, when added to beverages and liquid foods, they must be finely sized so that they do not feel uncomfortable to the touch. Used in the form of a pulverized slurry. However, the size of crushable particles is limited to several microns, and although there is no problem in texture, sedimentation occurs over time, making it difficult to use for long-term stored foods and short-term stored foods. There is also a problem that the use is restricted. As a method for solving such a problem of sedimentation, Japanese Patent Laid-Open No.
No. 289877 discloses a method of synthesizing a hydroxyapatite (a kind of calcium phosphate) of 500 nm or less and treating the surface with a solution containing citric acid or a salt thereof, a protein such as casein or albumin, or a peptide such as casein phosphopeptide. It has been disclosed. According to this method, although the effect of suppressing sedimentation is recognized, its effect is hardly sufficient, and since it may change the taste when added to food, the dispersibility is further improved and the taste is improved. A calcium filler that has no effect was desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a calcium compound fine particle of the order of nanometers which is uniformly dispersed without causing aggregation, separation, sedimentation, etc., and contains a carboxyl group which does not affect the taste. Polysaccharide /
An object of the present invention is to provide a calcium reinforcing agent containing a calcium compound complex. Another object of the present invention is to provide a calcium reinforcing agent containing a citrate / calcium compound composite having improved dispersion stability.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by using a polysaccharide containing a carboxyl group, calcium compound fine particles which are hardly soluble in water can be obtained. The present inventors have found that they are stably dispersed, leading to the present invention. In addition, while studying a method of stabilizing this complex, when a calcium compound that is hardly soluble in water is synthesized in the presence of a polysaccharide having a carboxyl group, the particle morphology of the calcium compound changes, and the dispersibility greatly increases. It was found to be improved. By applying this to citrate, which was conventionally reported to have an effect on dispersion stability, it was found that the dispersion stability was dramatically improved compared to the case of simply mixing and surface-treating. .

That is, the present invention provides (1) a polysaccharide having a carboxyl group in a molecule thereof and water-soluble calcium compound fine particles having a particle diameter of 500 nm or less in a weight ratio of 10:90.
９９99.9: a calcium reinforcing agent characterized by containing a polysaccharide / calcium compound complex containing in the range of 0.1; (2) in a water-based medium of a polysaccharide containing a carboxyl group in a molecule; (1) The calcium reinforcing agent according to (1), which contains a dispersion solution of a polysaccharide / calcium compound complex excellent in dispersion stability, which is obtained by dispersing calcium compound fine particles having a particle diameter of 500 nm or less and is insoluble in water. , (3)
The calcium compound insoluble in water is calcium carbonate or calcium phosphate, wherein the calcium reinforcing agent according to (1) or (2), and (4) calcium phosphate is produced by reacting calcium hydroxide with phosphoric acid. (5) The calcium reinforcing agent according to (3), wherein the polysaccharide / calcium compound complex is obtained by producing a calcium compound in the presence of a carboxyl group-containing polysaccharide. (1)-
(6) The calcium reinforcing agent according to any one of (1) to (4), wherein the calcium compound is produced in the presence of a carboxyl group-containing polysaccharide. (7) A citrate / calcium compound composite having excellent dispersion stability, wherein finely dispersed calcium compound fine particles having a particle diameter of 500 nm or less are dispersed in an aqueous medium of citrate. Calcium containing a citrate / calcium compound complex, characterized by containing a body dispersion solution, wherein the dispersion solution is obtained by producing a calcium compound in the presence of citrate. (8) The method for producing a calcium reinforcing agent according to (7), wherein the calcium compound is produced in the presence of a citrate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The calcium reinforcing agent of the present invention comprises a polysaccharide or a citrate having a carboxyl group in the molecule and water-insoluble calcium compound fine particles having a particle size of 500 nm or less in a weight ratio of 10%. : 90 to 99.9: 0.1, characterized by containing a polysaccharide or a citrate / calcium compound complex.

The carboxyl group-containing polysaccharide used in the present invention includes those derived from nature and those obtained by modifying natural polymer materials (semi-synthetic polymer compounds). Polysaccharides containing a carboxyl group derived from nature are compounds having uronic acids such as glucuronic acid, galacturonic acid and mannuronic acid in the molecule, gum arabic, sodium alginate, pectin, sodium chondroitin sulfate, sodium hyaluronate, heparin, etc. Is exemplified. Semi-synthetic polymer compounds include those obtained by modifying natural polysaccharides such as sodium carboxymethylcellulose, sodium carboxymethyl chitin, and sodium carboxymethyl starch, and those obtained by graft copolymerization of acrylic acid with polysaccharides such as starch and cellulose. can give. It is preferable that the carboxyl group contained in these polysaccharides is usually a salt of an alkali metal such as sodium or potassium. The carboxyl group does not need to be completely in the form of a salt, and may be an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid, or an organic acid such as citric acid, fumaric acid, malic acid, or acetic acid that can be used for food addition. By adding and adjusting the pH of the aqueous solution, there is no problem even if some exist as an acid form.

The citrate used in the present invention is:
Alkali metal salts such as monosodium citrate, disodium citrate, trisodium citrate, monopotassium citrate, dipotassium citrate, and tripotassium citrate are preferably used, and the inorganic or organic acids described above. Alternatively, those having various degrees of neutralization by adding an alkali such as sodium hydroxide or potassium hydroxide to adjust the pH of the aqueous solution may be used.

The water-insoluble calcium compound fine particles of the present invention are not limited as long as they have a particle size of 500 nm or less. However, considering that they are ingested into the body as foods, calcium phosphate or calcium phosphate used as a natural calcium source is used. Calcium carbonate is preferred.

In the present invention, the polysaccharide (or citrate) / calcium compound complex comprises the above-mentioned carboxyl group-containing polysaccharide (or citrate) and calcium compound fine particles in a weight ratio of 10:90 to 99.99. 9: 0.
1, preferably 15:85 to 99.5: 0.5, more preferably 20:80 to 99: 1.
If the amount of the calcium compound is less than 0.1%, the effect of adding the calcium compound is poor, and if it exceeds 90%, the dispersion stability is poor, sedimentation and separation are likely to occur, and a uniform dispersion solution cannot be formed. Absent.

As a method for synthesizing calcium compound fine particles, a liquid phase synthesis method is preferable. This is a so-called precipitation method, in which an organic acid, an inorganic acid and salts thereof are reacted with an aqueous solution or suspension of a water-soluble or hardly-soluble calcium compound to form a hardly water-soluble calcium compound fine particle. Synthesized. As called the precipitation method,
Usually, the produced water-insoluble inorganic fine particles are precipitated, filtered, and dried or thermally decomposed to obtain a powder.

In the present invention, the carboxyl group-containing polysaccharide is mixed with a poorly water-soluble calcium compound suspension produced by a precipitation method, and the suspension is subjected to a physical method such as mechanical stirring or ultrasonic irradiation. A polysaccharide / calcium compound complex and a dispersion solution with reduced sedimentation / separation can be produced. However, in this method, it may be difficult to uniformly disperse aggregates of relatively large particles or primary particles which are easily generated in the production by the precipitation method without sedimentation. In that case, it is only necessary to remove the components that settle at the beginning and use only the upper layer. To further improve dispersion stability,
When synthesizing a poorly water-soluble calcium compound, a method of synthesizing a calcium compound by using a polysaccharide containing a carboxyl group (in-situ method) is used. Fine particles generated by this method do not precipitate,
The resulting dispersion is a polysaccharide / calcium compound composite dispersion that is uniformly dispersed in a colloidal form and has extremely excellent dispersion stability. The reason why such a polysaccharide / calcium compound composite dispersion having excellent dispersion stability is obtained is not always completely elucidated, but it is presumed that the following mechanism is most likely.

The present inventors have shown that there is an ionic bond between a calcium ion of a calcium compound and a carboxyl group of a polysaccharide based on the experimental fact of dispersion stability against pH and ionic strength. It is considered that such an interaction exists also in the reaction process by the in-situ method, and it is sufficiently considered that the calcium compound generated by the reaction adsorbs a polysaccharide containing a carboxyl group in the growth process. It is considered that the polysaccharide thus adsorbed on the calcium compound inhibits the crystal growth of the calcium compound, and the particle diameter does not become 500 nm or more. In this case, if the growth direction is affected by the adsorbed polysaccharide, the morphology of the particles changes, and the dispersibility may be further improved. For example, it has been confirmed by transmission electron microscopy that the primary particles of hydroxyapatite are usually acicular, but become flat particles when synthesized in the presence of a polysaccharide. As described above, the effect of suppressing aggregation due to the change in particle shape is one of the factors that improve dispersibility.
One. Also, the 500 nm thus generated
In the following water-insoluble calcium compound fine particles, aggregation between the fine particles is suppressed because the polysaccharide bonded to the calcium compound exhibits a protective colloidal action, and as a result, the dispersion state is stably maintained without causing aggregation for a long time. It is considered something. In other words, the effect of the polysaccharide is brought about by (1) inhibition of crystal growth, (2) change in particle morphology, (3) inhibition of inter-particle aggregation, or any or all of these effects of the calcium compound. It can be rationally explained that those produced by the in-situ method have better dispersibility.

In the case of a calcium reinforcing agent containing the citrate / calcium compound complex of the present invention, a method of synthesizing a calcium compound by allowing a citrate to be present when synthesizing the calcium compound ( in-
(situ method). The compound formed by this method becomes a citrate / calcium compound composite dispersion having extremely excellent dispersion stability, which is uniformly dispersed in a colloidal form without precipitation. This method can be explained by the same mechanism as that of polysaccharides.Citrate not only modifies the surface of particles but also has the effect of changing the particle morphology if it is present during the production of particles, so that it is stable. It is considered that a composite dispersion having improved properties can be produced.

Examples of the calcium compound used for synthesizing the calcium compound fine particles of the present invention include calcium chloride, calcium acetate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium lactate, calcium citrate, and calcium gluconate. And at least one compound selected from calcium hydroxide, calcium carbonate, calcium chloride, calcium nitrate, calcium sulfate, calcium thiosulfate and the like.

The inorganic acid, organic acid and salts thereof used in the synthesis of the calcium compound fine particles of the present invention may be any as long as they react with the above-mentioned calcium compound to form calcium compound fine particles which are hardly soluble in water. Above all, carbonic acid,
Phosphoric acid (orthophosphoric acid), formic acid, acetic acid, propionic acid,
Examples thereof include butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, lactic acid, malic acid, tartaric acid, and hydrochloric acid, and alkali metal salts and alkaline earth metal salts thereof.

The case where the calcium compound fine particles are calcium phosphate will be described in detail below.

In the present invention, calcium phosphate has a total of 50% by weight of a portion derived from phosphoric acid and calcium atoms.
These are included. Examples include hydroxyapatite, fluoroapatite, chlorapatite, carbonate-containing apatite, magnesium-containing apatite, apatite compounds such as iron-containing apatite, and tricalcium phosphate.

The basic composition of the apatite compound contained in the calcium phosphate of the present invention is represented by M _x (RO ₄ ) _y X _z . When the M site is a calcium ion (Ca ²⁺ ), the RO ₄ site is a phosphate ion (PO ₄ ³⁻ ), and the X site is a hydroxide ion (OH ⁻ ), x = 10, y = 6, z = 2
Which is a compound generally called hydroxyapatite. Each site of M, RO ₄ , and X can be replaced with various ions and the like, and can also be vacancies. The amount of substitution and the amount of vacancies vary depending on the type of the ion or the like. A hole may be used.

The portion derived from phosphoric acid and the calcium atom
If the total is less than 50% by weight, calcium phosphate
It is not preferable because properties may be lost. M rhino
Is basically Ca²⁺But replaced with various metal ions
It is known that it can be done. Io replaceable for food applications
For example, H⁺, Na⁺, K⁺, H_ThreeO⁺, C
r^{Two +}, Zn²⁺, Mg²⁺, Fe²⁺, Mn²⁺, Ni²⁺, Cu
²⁺, Fe³⁺, Co²⁺And the like. Thus, Ca
²⁺Replace and introduce the necessary amount of biologically essential trace elements
Both are possible. RO_FourSite is basically PO_Four ^3-Is
Is an example of a replaceable ionic species,_Four ^2-, C
O_Three ^2-, HPO_Four ^2-, H_FourO_Four ^Four-And the like. X site
Examples of ionic species and molecules that enter^-, Cl^-,
I^-, O^2-, CO_Three ^2-, H_TwoO and the like.

The particle size of calcium phosphate contained in the calcium reinforcing agent of the present invention is 500 nm or less. If the particle size exceeds 500 nm, the particles are liable to settle and separate, and the stability of the dispersion solution is poor. The calcium phosphate crystal structure may be any, and may be amorphous. Further, the shape of the calcium phosphate is not particularly limited, and may be any shape such as a sphere, a needle, a column, and an irregular shape. Regarding particle size distribution,
There is no particular limitation as long as the particle size is 500 nm or less. The particle size used here indicates the major axis diameter of the particle.

The calcium phosphate may be produced by any method, but a so-called wet method (liquid phase method / precipitation method) is preferred. The wet method is a method of synthesizing calcium phosphate by mixing an aqueous solution of a calcium compound (suspension) and an aqueous solution of phosphoric acid or phosphate. Generally, both solutions are dropped simultaneously or the other solution is put into one solution. The method of dropping the solution is adopted. The dropping time is not particularly limited, but is generally about 5 minutes to 24 hours. After completion of the dropwise addition, the reaction is aged, if necessary.

The method of preparing a carboxyl group-containing polysaccharide / calcium phosphate composite dispersion having excellent dispersion stability includes the above-mentioned mechanical mixing and dispersion method and the method of preparing calcium phosphate in the presence of a carboxyl group-containing polysaccharide. Although there is a manufacturing method (in-situ method), the latter method is preferable.

In the in-situ method, the polysaccharide containing a carboxyl group may be present in a reaction solution in which calcium phosphate is formed, and is mixed with an aqueous solution of a calcium compound (suspension) or an aqueous solution of phosphoric acid or phosphate. Or both may be mixed. Moreover, you may add continuously and intermittently to a reactor independently from both.

Examples of the calcium compound used for synthesizing the calcium phosphate of the present invention include the compounds used for synthesizing the calcium compound described above.

The phosphoric acid or phosphate used in the present invention includes phosphoric acid (orthophosphoric acid), calcium monohydrogen phosphate, calcium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium These include sodium and potassium salts other than salts. Organic or inorganic salts other than the target compound, which are by-produced during the reaction, need to be removed depending on the use. In that case, desalting is performed by a known method such as dialysis. When calcium phosphate is used as the target compound, it is particularly preferable to use calcium hydroxide and phosphoric acid or calcium carbonate and calcium monohydrogen phosphate as raw materials since no by-product salt is generated. In addition, it is known that, among calcium phosphates, those having an apatite structure can be replaced with various ions as described above because of the flexibility of the structure, and a compound containing an ionic species other than calcium and phosphate is used in combination as necessary. You can also.

Usually, the reaction is carried out by keeping the reaction solution at a predetermined temperature. It is not necessary to maintain the same temperature during the reaction, and the temperature may be appropriately changed as the reaction proceeds. The reaction is performed while heating or cooling as necessary. Since the size of the calcium phosphate particles generated by the reaction temperature changes, the particle size can be changed by changing the reaction temperature, and as a result, the transparency of the film prepared from the aqueous dispersion solution can be adjusted. The reaction temperature is generally in the range of 5-95C. The atmosphere in the reactor is not particularly limited and is usually carried out in air. However, in order to control the composition of calcium phosphate, it is better to substitute an inert gas such as nitrogen gas. The synthesis time is not particularly limited, but is generally about 1 to 120 hours in total for the time of dropping and aging.

The stirring method is not particularly limited as long as it is a method of uniformly mixing.
Examples include a method using ultrasonic waves. When a batch-type reaction vessel using a stirring blade is used, it cannot be said unconditionally because it is affected by the shape of the stirring blade, the solution viscosity, and the like, but the stirring speed is generally in the range of 30 to 10,000 rpm.

Water is used as the reaction solvent, but organic solvents such as ethanol and glycerin used in food applications may be used in combination.

The concentration at the time of synthesis is not particularly limited, but is generally in the range of 0.5 to 60% by weight in total with the solid content of calcium phosphate and polysaccharide containing a carboxyl group.
Preferably it is in the range of 1 to 50% by weight. If it exceeds 50% by weight, the viscosity of the dispersion may increase, and handling may be difficult.

Since the type of calcium phosphate produced differs depending on the pH at the time of the reaction, the production of a specific species may be performed while adjusting the pH. The pH can be adjusted with sodium hydroxide, potassium hydroxide or the like. In particular, when the target compound dissolves due to a change in pH, or when the complex is separated due to a change in the dissociation state of the carboxyl group, it is necessary to strictly adjust the pH. For example, in the case of hydroxyapatite (calcium phosphate), p
It is adjusted by adding an alkali appropriately so as not to become H5 or less.

The carboxyl group-containing polysaccharide / calcium phosphate composite dispersion thus obtained, which is excellent in stability, is a uniform emulsion solution and does not cause sedimentation or separation even when left for a long time. The term "excellent in stability" as used herein means that the volume of sedimentation or separation at a calcium compound concentration of 0.5% is 3 vol% or less after one week.

When the calcium compound fine particles which are hardly soluble in water are calcium carbonate, they are produced in the same manner as calcium phosphate. In this case, the same raw material as calcium phosphate can be used as the calcium source, and
Carbon dioxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate and the like are appropriately used. As in the case of calcium phosphate, a combination of calcium hydroxide and carbonic acid (gas) is preferable in order not to generate by-product salts.

The calcium reinforcing agent of the present invention is produced in the form of an emulsion in which a water-insoluble calcium compound is dispersed in an aqueous dispersion medium by the above-mentioned method. This emulsion can be added to food as it is, but depending on the intended use, emulsifiers such as sucrose fatty acid ester, sorbitan fatty acid ester, lecithin, antioxidants such as ascorbic acid and tocophenol, various (multi) Sugars,
Various amino acids, proteins such as collagen, gelatin, casein and albumin, various vitamins, food acids such as gluconic acid, malic acid, and citric acid, polyhydric alcohols such as glycerin, preservatives such as potassium sorbate, preservatives, etc. May be added.

The calcium reinforcing agent of the present invention is obtained by removing water from the carboxyl group-containing polysaccharide / calcium compound complex or citrate / calcium compound complex having excellent dispersion stability thus obtained. It is also possible to solidify. Depending on the application, the composite
It can be processed into an arbitrary shape such as a film, a sheet, a powder, a foam, and a thread by using a known method or equipment.

It is also possible to process into a gel by a method of physically forming a crosslinked structure by a temperature change or a method of forming a crosslinked structure by a chemical bond (ionic bond or covalent bond) using a crosslinking agent. It is.

For example, in the case of processing into a film, the aqueous dispersion solution is used as it is, or a concentration treatment, pH adjustment, a plasticizer such as glycerin, a crosslinking agent, a thickener,
After mixing additives such as coloring agents and antioxidants, the above stable dispersion is applied and formed on a substrate such as glass, quartz, metal, ceramics, plastic, and rubber, a roll, a belt, and the like, If necessary, it can be produced by performing a treatment such as heating, decompression, air supply, infrared irradiation, or ultrashort wave irradiation to evaporate water and / or an aqueous solvent. There is no particular limitation on the application method, a flow coating method, a dipping method,
There are spray method, bar coater, spin coater,
Known coating machines such as a knife coater, a blade coater, a curtain coater, a gravure coater, and a spray coater can be used. The coating thickness (thickness before drying) is approximately 1
The thickness can be arbitrarily set in the range of μm to 10 mm by selecting a coating method. The temperature for evaporating water and / or the aqueous solvent is in a temperature range of 0 to 150 ° C., and the pressure is reduced to normal pressure or reduced pressure. At that time, the drying time can be shortened by flowing dry air or dry nitrogen. Further, when a crosslinking reaction is promoted for the purpose of imparting water resistance, for example, 4
The heat treatment is performed at 0 to 200 ° C. for several seconds to several tens minutes. When the film is peeled off from the base material, the use of a plastic base material provides good releasability, but when other base materials are used, a known release property may be applied to each material as necessary. It is preferable to apply a mold agent in advance. The film produced in this way has a feature of excellent transparency. This indicates that the size of the calcium phosphate fine particles is not more than the wavelength region of visible light, and that the individual particles are uniformly dispersed in the polymer matrix without causing aggregation.

The method of pulverizing the complex from the carboxyl group-containing polysaccharide / calcium compound complex dispersion solution can be carried out in the same manner as in the film processing, by using the aqueous dispersion of the complex as it is, or by performing a concentration treatment, pH adjustment, and if necessary. After mixing additives such as a plasticizer such as glycerin, a crosslinking agent, a thickener, a coloring agent, and an antioxidant, a method of directly vaporizing a solvent from a dispersion liquid such as spray drying or freeze drying, or A method of performing a solid separation treatment by using an organic solvent such as methanol which is miscible with water but not dissolving the complex or a compound having a high salting-out effect such as sodium sulfate, drying and pulverizing is also possible.

As for other shape processing, as in the case of film processing, the dispersion solution of the complex is used as it is, or is subjected to concentration treatment, pH adjustment, and if necessary, a plasticizer such as glycerin, a crosslinking agent, a thickener, a coloring agent. After mixing additives such as an agent, an antioxidant and a heat stabilizer, it can be carried out by a known method.

Since the calcium reinforcing agent of the present invention is tasteless and odorless and has no effect on the taste of the food to be added, it can be added to various foods. Among them, it is most useful when added to liquid foods because of its excellent dispersibility in water, but it is added to solid foods because it can be processed into films and powders. It is also possible.

Examples of the liquid food in which the calcium reinforcing agent of the present invention is used include milk, processed milk, milk drink, fermented milk, lactic acid drink, fruit juice, vegetable juice, coffee, black tea, green tea, barley tea, and oolong tea. , Wild grass tea, cocoa, soy milk, shiruko, soft drink, oral liquid, miso soup, soup, dressing, liquid seasoning, etc., and are not limited to these examples, but can be used in a wide range.

Examples of solid foods to which the calcium supplement of the present invention is used include processed meats such as cheese, pudding, jelly, bread, noodles, ham and sausage, processed vegetables such as pickles and dried vegetables, and processed foods. There are fish, cooked rice, bean paste, yokan, creams, chocolate and gum, caramel, cookies, rice crackers, candy, popcorn, potato chips and other confectionery, powdered milk, solid seasonings, etc., and are limited to these examples. It can be widely used for general foods.

Further, it can be used for pharmaceutical applications such as tablets, granules and liquids, and also for feeds such as feed additives, compound feeds and pet foods.

The calcium supplement of the present invention can be ingested without affecting the original texture and taste of food even when added to food, and can be precipitated for a long time even when added to liquid food or drink. It does not disturb the flavor and the like of the food because it is dispersed stably.

[0046]

Hereinafter, the present invention will be described in detail with reference to Examples.
The present invention is not limited to these examples. Further,% used in the following examples is based on weight unless otherwise specified. Analysis by X-ray diffraction is RINT X-ray D
The measurement was performed using an iffractometer (manufactured by Rigaku Denki Co., Ltd.). FT
-IR measurement was performed using FT / IR-8300 Fourier transform infrared spectrophotometer manufactured by JASCO Corporation. Transmission electron microscope (TEM) observation was performed using an H-300 type Hitachi electron microscope (manufactured by Hitachi, Ltd.).

Production Example 1 18.44 g of calcium hydroxide (Kanto Chemical Co., high-purity reagent, 3N) and distilled water 58 were placed in a round-bottom separable flask equipped with a stirrer, thermometer, and pH meter.
1.56 g was added and stirred vigorously to form a suspension. After adjusting the temperature of the suspension to 40 ° C., 75% phosphoric acid (manufactured by Mitsui Chemicals, Inc.)
An aqueous solution obtained by mixing and dissolving 153.66 g of an aqueous solution diluted with 10.6% and 246.34 g of distilled water was continuously added over 2 hours using a microtube pump. After the addition, the reaction was further performed at 40 ° C. for 2 hours to obtain a calcium phosphate fine particle dispersion. This reaction was performed twice under the same conditions. When these reaction solutions were left overnight, 50 vol% of each of them settled out. The supernatant was discarded, the two solutions were mixed, and the mixture was allowed to stand for 2 days to remove the separated supernatant, thereby preparing an untreated calcium phosphate dispersion slurry. The solid content of this slurry was 6.24%, and further separation was observed after long-term storage. However, in the following tests, the slurry was mixed and dispersed well before use.

[Compounding Example 1] In a round-bottom separable flask equipped with a stirrer and a thermometer, 5.089 g of citric acid monohydrate (manufactured by Junsei Chemical Co., Ltd., special grade) was added, and 133.40 g of distilled water was uniformly stirred and dissolved. After adding 6.90 g of a 40% aqueous sodium hydroxide solution and 1.84 g of a 10% aqueous sodium hydroxide solution, pH was added.
Was adjusted to 8.30. 4.61 g of calcium hydroxide (manufactured by Kanto Chemical Co., high purity reagent, 3N) was added with stirring to form a suspension. The temperature of the suspension was adjusted to 40 ° C, and while stirring at a stirring speed of 300 rpm, 34.57 g of a 10.5% phosphoric acid aqueous solution and 65.
The aqueous solution mixed with 43 g was continuously added by a micro tube pump over 2 hours. After the addition, the mixture was further reacted at 40 ° C. for 2 hours to obtain a sodium citrate / calcium phosphate composite (50:50) dispersion solution (a-1). The pH of the resulting dispersion was 12.22, and almost no sediment was formed. The amount of sediment produced was greatly reduced as compared with the composite comparative example 1. It was stable without any change such as separation or sedimentation even after standing for several weeks. The solid content of this dispersion was 5.50%.

[Composite Example 2] 20.03 g of the calcium phosphate dispersion slurry obtained in Production Example 1, 12.53 g of an aqueous solution (9.98%) of carboxymethylcellulose (CMC: cellogen F-5A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) After mixing and dissolving 17.55 g of distilled water, ultrasonic irradiation was performed at room temperature for 90 minutes.
Immediately after the treatment, a good dispersion solution (b-1) was given, but there was a component that settled in a relatively short period of time, and when left at room temperature for one week, a sediment of about 2.5 vol% with respect to the liquid amount was recognized. . However, the calcium phosphate slurry without the addition of CMC completely separated and settled to produce a clear supernatant,
The dispersion treated with CMC was an entirely cloudy emulsion, and when the precipitate formed at the initial stage was removed, no further precipitate was formed and the dispersion was present as a stable dispersion. The sediment was easily redispersed only by light stirring.

[Compounding Example 3] Carboxymethylcellulose (CMC: Cellogen F-) previously dissolved in distilled water in a round bottom separable flask equipped with a stirrer and a thermometer was used.
5A; Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution (4.90%) 102.
After adding 04g and 14.27g of distilled water and mixing uniformly, 3.688g of calcium hydroxide (manufactured by Iriko Sangyo) was added with stirring to form a suspension. The temperature of the suspension was adjusted to 40 ° C and the stirring speed was 30
While stirring at 0 rpm, an aqueous solution obtained by mixing 27.82 g of a 10.5% phosphoric acid aqueous solution and 52.18 g of distilled water was continuously added over 2 hours by a microtube pump. After addition, at 40 ° C 2
Reaction was performed for a time, and a carboxymethylcellulose / calcium phosphate composite (50:50) dispersion solution (c-1) was obtained.
I got The pH of the resulting dispersion was 11.60, and almost no sediment was formed. Example 2 of compounding
The amount of sediment produced was significantly reduced as compared to. It was stable without any change such as separation or sedimentation even after standing for several weeks. This composite dispersion is applied to an IR window plate (KRS-
FIG. 1 shows the IR spectrum of the film directly cast in 5). FIG. 2 shows an XRD spectrum of a sample obtained by powdering the dispersion solution by freeze-drying. The results of FIGS. 1 and 2 show that this dispersion solution is composed of CMC and hydroxyapatite. FIG. 3 shows a transmission electron micrograph taken by diluting this dispersion solution and drying it on a collodion film-coated copper mesh. This figure shows that hydroxyapatite particles having a particle size of about 100 nm are dispersed without aggregation. Further, 100.03 g of the reaction solution was taken for use in a test for food addition, and stirred at room temperature for 1 hour.
0.5% phosphoric acid aqueous solution was added dropwise to adjust the pH to 7.02.
The required amount of phosphoric acid was 1.336 g, and the Ca / P ratio at this time was 1.52. Dispersed aqueous solution (c-
The solid concentration of 2) was 5.0%.

[Comparative Comparative Example 1] 20.0 g of the calcium phosphate dispersion slurry obtained in Production Example 1, 1.42 g of trisodium citrate dihydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), 28.
After mixing and dissolving 55 g, ultrasonic irradiation was performed at room temperature for 90 minutes. Immediately after the treatment, some sediment was observed, and when left at room temperature for one week, about 10 vol% of sediment based on the liquid amount was observed. When left at room temperature for another month, a clear supernatant liquid was separated.

[Addition test to milk] A total of 100.0 g of commercial milk (Meiji Hokkaido Milk Brick LL, storable at room temperature) was mixed with 10.0 g of the additive and distilled water, left at room temperature for 5 hours, and then cooled at 5 ° C. , And observed over time. The amount of hydroxyapatite contained in the additive was set to 250 mg (100 mg as Ca). (1) Blank test: Change was pursued by adding only 10.0 g of distilled water. The pH after 5 hours was 6.74. Little change was observed, and the solution was turned upside down after 10 days, leaving only a white thin film. (2) Untreated product: 4.02 g of the calcium phosphate dispersion slurry obtained in Production Example 1 and 5.98 g of distilled water were added to follow the change. After 5 hours, the pH was 6.67. 3.6vol 5 hours later
%, And then gradually changed to a dark white precipitate. After 10 days, about 4.8 vol% of the precipitate was observed. (3) CMC-treated product: Compounding 10.0 g of the dispersion solution (c-2) obtained in Example 3 was added to follow the change. After 5 hours, the pH was 6.70. Little change observed, 1
When the solution was turned over after one day, a white thin film was observed. Even after 10 days, the thin film became very dark, but a clear difference from the blank test could not be distinguished.

[Rice Cooking Test] Two sets of milled rice (Akitakomachi) were washed well several times using a whisk and a colander, and after thoroughly draining the colander, 400 ml of tap water was added. 20.0 g of the obtained dispersion liquid (c-2) was added and mixed, and rice was cooked in a home rice cooker mode. This is a condition under which 100 mg of Ca is added per milled rice. The cooked rice was glossy, and no difference was observed in texture and taste as compared with the non-added type.

[0054]

The calcium supplement of the present invention is extremely stable in water and hardly affects the texture and taste. Can be suitably used without causing the Further, since the calcium reinforcing agent of the present invention can be used for solid foods without any problem and can be processed into films, powders, and the like, it can be used in a form different from conventional ones, and the range of applications is greatly expanded.

[Brief description of the drawings]

FIG. 1 shows I of a composite dispersion solution (c-1) according to the present invention.
It is an R spectrum figure.

FIG. 2 is an XRD spectrum of a sample obtained by freeze-drying the complex dispersion solution (c-1) according to the present invention.

FIG. 3 is a transmission electron micrograph taken by diluting the composite dispersion solution (c-1) according to the present invention and drying the diluted solution on a copper mesh covered with a collodion membrane.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 47/12 A61K 47/12 47/36 47/36 A61P 3/02 A61P 3/02 // B01F 17 / 38 B01F 17/38 17/56 17/56 F term (reference) 4B018 MD04 MD33 MD35 ME14 MF10 4C076 AA22 BB01 CC40 DD43F EE30F FF16 FF43 4C086 AA01 HA04 HA16 HA19 MA02 MA05 MA23 MA52 NA03 ZC21 4D077 AA02 CA08 DA05 DC26Y DC28Y DD65Y DE07Y DE10Y DE13Y

Claims (8)

[Claims] 1. A polysaccharide containing a carboxyl group in a molecule and water-insoluble calcium compound fine particles having a particle size of 500 nm or less in a weight ratio of 10:90 to 99.9: 0.1. A calcium reinforcing agent comprising a polysaccharide / calcium compound complex. 2. A polysaccharide / calcium compound composite having excellent dispersion stability, obtained by dispersing a water-insoluble calcium compound fine particle having a particle size of 500 nm or less in an aqueous medium of a polysaccharide containing a carboxyl group in the molecule. The calcium reinforcing agent according to claim 1, comprising a body dispersion solution. 3. The calcium reinforcing agent according to claim 1, wherein the calcium compound hardly soluble in water is calcium carbonate or calcium phosphate. 4. The calcium reinforcing agent according to claim 3, wherein the calcium phosphate is produced by reacting calcium hydroxide and phosphoric acid. 5. The polysaccharide / calcium compound complex is obtained by producing a calcium compound in the presence of a carboxyl group-containing polysaccharide. Calcium supplement. 6. The method for producing a calcium reinforcing agent according to claim 1, wherein the calcium compound is produced in the presence of a polysaccharide containing a carboxyl group. 7. A particle size of 500 n in an aqueous medium of citrate.
m, which contains a citrate / calcium compound composite dispersion having excellent dispersion stability, which is obtained by dispersing calcium compound fine particles insoluble in water of not more than m. A calcium reinforcing agent containing a citrate / calcium compound complex, which is obtained by producing a calcium compound. 8. The method for producing a calcium reinforcing agent according to claim 7, wherein the calcium compound is produced in the presence of a citrate.