KR100407079B1 - Feed additives for aquatic animal husbandry containing novel phosphoric acid amino acid polyvalent metal complex salts - Google Patents

Abstract

The present invention is safe and economical, contains basic amino acids (and other biologically active substances), does not elute basic amino acids in water, elutes the basic amino acids in the digestive organs of aquaculture aquatic animals, which efficiently digest and absorb them As a composition, a composition in powder or granule form is provided.

The composition of the present invention is a phosphate amino acid polyvalent metal complex salt consisting of basic amino acid, alkaline earth metal (and polyvalent metal other than magnesium) and phosphoric acid, which is insoluble in neutral to alkaline water and soluble in acidic water. It is a feed additive composition for aquatic animal breeding, containing at least one kind of, can be made by dispersing other biologically active substances, and can be prepared in the form of granules.

Description

Feed additive composition for aquatic animal breeding containing novel phosphate amino acid polyvalent metal complex salt

The present invention relates to a feed additive composition for aquatic animal breeding containing a phosphoric acid amino acid polyvalent metal complex salt as an active ingredient. More specifically, the feed additive composition for aquatic animal breeding in the form of powder or (homogeneous) granules containing the complex salt and stable in seawater and freshwater and capable of releasing basic amino acids in the digestive organs of aquatic animals. It is about.

About half of the feed used in aquaculture breeding of aquatic animals, such as fish such as defense, sea bream and eel, and aquaculture such as shrimp and oyster, is a compound feed, and the other half is a biological feed such as frozen sardine. Among these, biological feeds have a low predation rate by aquatic animals, and most of them feed in water, which may lead to environmental pollution or environmental destruction. In addition, biological feeds tend to be gradually depleted of their resources, have large price fluctuations, and are disadvantageous in terms of cost. On the other hand, compound feeds can be obtained from plant sources, but in this case, amino acid balance does not necessarily meet the needs of aquaculture animals, and in particular, basic amino acids are often deficient.

In addition, when biologically active substances such as amino acids and vitamins are added to a blended feed and administered to aquaculture animals, most of the biologically active substances are soluble in water and are dissolved, which makes it difficult to effectively use them. . Therefore, a feed additive composition for aquatic animal breeding that can protect these biologically active substances from being eluted in water and can be digested and absorbed in the digestive organs of aquatic animals is important in the fields of aquatic animal feed, nutritional supplements, animal medicines and the like. .

As a feed additive composition for aquatic animal breeding containing a biologically active substance, what coat | covered the nucleus containing a biologically active substance with hydrophobic substances, such as fats and oils, has been proposed previously. As a method for coating a biologically active substance with a hydrophobic protective substance, for example, Japanese Patent Application Laid-Open No. 4-173060 discloses coating a water-soluble amino acid and / or a water-soluble amino acid derivative with a fat or oil of solid animal or animal fat or wax at room temperature. The method is proposed as a manufacturing method of aquatic feed raw material.

However, the feed additive composition for aquatic animal breeding obtained by coating a nucleus containing a biologically active substance with a hydrophobic protective substance is mixed or granulated with other blended feed ingredients from the viewpoint of formulated feed production, which has been flourishing in recent years. The breakage of mechanical granules and / or coatings occurs, and the protective properties in water are often impaired, and the feed additive composition cannot be said to be versatile. In addition, in the case of administering the coated particles alone, there is a problem in that the palatability of the aquaculture animal is not sufficient and a necessary amount cannot be ingested.

As such, in order to be a feed additive composition that can withstand the mixing and granulation with other blended feed ingredients, it is itself a powder or (homogeneous) granules, which prevents the release of biologically active substances in the water and also digests aquatic animals. It is desirable to have the property to elute biologically active substances in the organ. However, when basic amino acids are used for nutritional improvement of feed, substances containing basic amino acids as powders or (homogeneous) granules, insoluble in neutral water and soluble in acidic fluids of the digestive tract, No tungstate salts were found.

In addition, Japanese Laid-Open Patent Publication No. 63-98357 discloses a ruminant feed additive composition formed by coating a salt of a basic amino acid with an acidic phosphate with a synthetic polymer, but among various salts of the invention, Salts of alkaline earth metal salts with basic amino acids have a molar ratio of phosphoric acid, alkaline earth metal salts and basic amino acids from 1: 0.5: 1 to 2, which are different from the complex salts of phosphoric acid, alkaline earth metals and basic amino acids of the present invention. Since the salt of the acidic alkaline earth metal salt and basic amino acid of the present invention rapidly decomposes in water, it produces a second phosphate of water-insoluble alkaline earth metal and a water-soluble basic amino acid first phosphate or a water-soluble basic amino acid second phosphate. This salt is substantially neutral and soluble in view of the solubility of the basic amino acid.

Phosphoric acid forms various salts with alkaline earth metals, some of which are insoluble in neutral to alkaline water and soluble in acidic water. For example, dibasic calcium phosphate and magnesium triphosphate are fermented with a lot of phosphoric acid. It is known to accumulate as a scale substance in an apparatus in industrial facilities, etc., and to cause an apparatus trouble. Magnesium ammonium phosphate has the same properties, but is substituted with an equivalent basic amino acid as a basic ion, consisting of phosphoric acid, alkaline earth metals and basic amino acids, 1 mole of phosphoric acid, 1 mole of alkaline earth metal and 1 mole of basic amino acid. The presence of tertiary phosphoric acid and / or second phosphate consisting of a complex salt (third phosphate salt) in proportion and a composition ranging from 1 to 1.45 moles of alkaline earth metal and 0.05 to 1 mole of basic amino acid relative to 1 mole of phosphoric acid is not known. . Moreover, in the alkaline earth metal salts of polyphosphoric acid and metaphosphoric acid, the presence of the phosphoric acid amino acid complex salt containing basic amino acid in the ratio of 0.02 to 0.3 to 0.7 to 0.98 in equivalence ratio with respect to alkaline earth metal is unknown.

Under the background of the above-mentioned prior art, the present invention is a composition containing basic amino acids in consideration of safety, economical efficiency, etc., which does not elute basic amino acids in water but elutes basic amino acids in the digestive organs of aquaculture animals, which is efficient. Compounds that are well digested and absorbed, or compositions containing these compounds, are intended to create compositions in the form of powder or (homogeneous) granules.

As a result of earnestly researching in order to achieve the above object, the present inventors have first found that various complex salts composed of basic amino acids, alkaline earth metals and phosphoric acid are insoluble and powdery insoluble in neutral to alkaline water and soluble in acidic water. It was found to have a form (Patent No. 6-306385 (WO96 / 17822)), and also a complex consisting of basic amino acid, magnesium and ortho phosphoric acid in the complex salt. Compound salts obtained by treating salts with (i) other divalent or trivalent polyvalent metal salts, (iia) using condensed phosphoric acid in combination with this, or (iib) condensed phosphoric acid and regular phosphoric acid in combination with these are neutral. More stable to inorganic ion-containing water such as to non-acidic water or seawater, that is, low solubility. Furthermore, these complex salts are insoluble in water and digestive organs of aquaculture animals. It found that combines an extremely excellent eluting at, and accomplished the present invention based on this knowledge.

That is, the present invention is a complex salt consisting of a basic amino acid, a polyvalent metal, and phosphoric acid, particularly, a phosphoric acid amino acid polyvalent metal complex salt which is insoluble in neutral to alkaline water represented by any one of the following Formulas 1 to 5 and is soluble in acidic water. It relates to a feed additive composition for aquatic animal breeding in the form of powder or granules, which contains as an active ingredient and, if desired, dispersed and contained other biologically active substances.

[Formula 1]

R _a M _b H _c PO ₄ ㆍ nH ₂ O

In Formula 1 above,

R is a basic amino acid hydrogen cation,

M is an alkaline earth metal,

a is 0.05 to 1,

b is 1 to 1.47,

c is 0 to 0.3,

a + 2 × b + c = 3,

n is from 0 to 10.

[Formula 2]

R _a M _b H _c PO ₄ (PO ₃ ) _m nH ₂ O

In Formula 2 above,

When phosphoric acid is polyphosphoric acid selected from pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, etc.,

R is a basic amino acid hydrogen cation,

M is an alkaline earth metal,

a is 0.02 × (m + 3) to 0.3 × (m + 3),

b is 0.35 × (m + 3) to 0.49 × (m + 3),

c is 0 to 0.2 × (m + 3),

m is 1 to 20,

a + 2 × b + c = m + 3,

n is from 0 to 10.

[Formula 3]

R _a M _b H _c (PO ₃ ) _m ㆍ nH ₂ O

In Formula 3 above,

When phosphoric acid is metaphosphoric acid selected from trimethic acid, tetramethic acid, hexamethic acid, etc.,

R is a basic amino acid hydrogen cation,

M is an alkaline earth metal,

a is 0.02 × m to 0.3 × m,

b is 0.35 × m to 0.49 × m,

c is 0 to 0.2 × m,

m is 3 to 50,

a + 2b + c = m,

n is 0 to 20.

[Formula 4]

R _a Mg _b M _c H _d PO ₄ ㆍ nH ₂ O

In Formula 4 above,

R is a basic amino acid hydrogen cation,

M is a polyvalent metal having a valence m other than magnesium, where m is the valency of the polyvalent metal being 2 or 3,

a is 0.05 to 1.0,

b is 0.85 to 1.43,

c is 0.02 to 0.6,

d is 0 to 0.3,

a + 2b + c × m + d = 3,

n is 0 to 20.

[Formula 5]

R _a Mg _b M _c H _d PO ₄ (PO ₃ ) _m ㆍ nH ₂ O

In Formula 5 above,

R is a basic amino acid hydrogen cation,

M is a polyvalent metal of valence q other than magnesium, where q is 2 or 3,

a is 0.05 to 0.4,

b is 0.90 to 1.47,

c is 0.01 to 1.4,

d is 0 to 0.3,

m is 0

a + 2 × b + q × c + d = m + 3,

n is from 0 to 10.

The present invention is described in detail below.

First, the phosphoric acid amino acid polyvalent metal complex salt represented by any of the above Formulas 1 to 4 will be described.

As a raw material phosphoric acid in the production of the phosphoric acid amino acid polyvalent metal complex salt of the present invention, in addition to the normal phosphoric acid, polyphosphoric acid, that is, diphosphoric acid (pyrophosphoric acid), tripolyphosphoric acid, tetrapolyphosphoric acid and other polyphosphoric acid, and trimethic acid, tetramethic acid , Hexametaphosphoric acid and other metaphosphoric acid, but the form of salts of phosphate, diphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, trimetaphosphoric acid, hexamethic acid and other metaphosphoric acid is excellent in terms of solubility, particularly preferably. Used. These can be used as it is or in the form of a (aqueous) solution of a suitable concentration.

As a raw material basic amino acid at the time of preparation of the said complex salt, 1 type, or 2 or more types of mixtures chosen from natural basic amino acids, such as lysine, arginine, ornithine, basic derivatives thereof, and basic derivatives of neutral amino acids are mentioned. Specifically, natural basic amino acids, such as lysine, arginine, ornithine; Basic derivatives such as basic amino acid-containing peptides; And basic derivatives of neutral amino acids such as amides and esters of amino acids such as methionine, tryptophan, threonine and the like. Among these, lysine and arginine are particularly preferably used because they are excellent in terms of nutritional value, economy and solubility of salts as essential amino acids.

In the present invention, examples of the alkaline earth metal constituting the phosphoric acid amino acid polyvalent metal complex salt represented by any one of Formulas 1 to 3 include magnesium, calcium, strontium, barium, and the like. Preferred in terms of biologically safe acceptance.

The phosphoric acid amino acid polyvalent metal complex salt of the present invention is a complex salt obtained as a crystal precipitate when basic amino acids, alkaline earth metals and phosphoric acid are coexisted in these aqueous solutions under relatively high concentrations of basic amino acids and in neutral to alkaline conditions. These complex salts are roughly classified into four types by the presence or absence of condensation of phosphoric acid, the form of condensation, and equivalent ratios of basic amino acids and alkaline earth metals when phosphoric acid is positive phosphoric acid. In addition, with respect to the phosphate amino acid complex metal salt in which phosphoric acid is regular phosphoric acid and alkaline earth metal is magnesium, the complex salt represented by the formula (4) containing, in addition to magnesium, other divalent or trivalent polyvalent metals is also the fifth type. Phosphoric acid amino acid polyvalent metal complex salt (to be described later) is included in the complex salt of the present invention.

Specifically, the phosphoric acid amino acid polyvalent metal complex salt of the first type of the present invention is a complex salt represented by the above formula (1), and 1 g equivalent of the basic amino acid hydrogen cation (R) and alkaline earth metal (M) to 3 g equivalents of phosphorous acid. 2 g equivalent and acid residue (H) Og equivalent ratio, n is theoretically 0, 1 or 2, but is 0 to 10 under dry conditions, the second type of complex salt of the present invention is also the formula It is a complex salt represented by 1, but unlike the first type, with respect to 3.0 g equivalent of regular phosphoric acid, 0.05-1.0 g equivalent of basic amino acid hydrogen cation (R), 2.0-2.94 g equivalent of alkaline earth metal (M) and acid residue ( H) is composed of a ratio of 0 to 0.3 g equivalents, n is 0 to 10, more preferably 0.05 to 0.8 g equivalents of basic amino acid hydrogen cation (R), alkaline earth metal (M) to 3.0 g equivalents of regular phosphoric acid 2.2-2.94 g equivalent and acid residue (H) 0-2. It is comprised by the ratio of 0.3 g equivalent, and n is 0-10. However, in Formula 1, a, b, and c have a relationship of a + 2 × b + c = 3.

The combined salts of the first and second types are preferably salts in which the alkaline earth metal is magnesium or calcium.

The phosphoric acid amino acid polyvalent metal complex salt of the third type of the present invention is a complex salt represented by the formula (2), and has a basic amino acid hydrogen cation (R) of 2 to 30 g equivalents to 100 g equivalents of polyphosphoric acid. M) is 70-98 g equivalents, and is comprised by the ratio of a + 2xb + c = m + 3, and n is 0-10.

The complex salt of the fourth type is a complex salt represented by the above formula (3), with respect to 100 g equivalents of metaphosphoric acid, 2 to 30 g equivalents of basic amino acid hydrogen cations (R), and 70 to 98 g equivalents of alkaline earth metals (M) Wherein the acid residue (H) is 0 to 20 g equivalents, and is constituted by a + 2b + c = m 100, and n is 0 to 20.

As for the 3rd and 4th type complex salt, the salt whose alkaline earth metal is magnesium or calcium is preferable.

Phosphoric acid amino acid polyvalent metal complex salt of the fifth type of the present invention is a complex salt represented by the formula (4), with respect to the complex salt wherein the alkaline earth metal is magnesium in the phosphate amino acid polyvalent metal complex salt represented by the formula (1), As a complex salt containing other divalent or trivalent polyvalent metals in addition to magnesium, by preparing a phosphate amino acid polyvalent metal complex salt composed of phosphate, basic amino acid and magnesium, and treating this with a polyvalent metal other than magnesium, It is a complex salt obtained by substituting some of the basic amino acid, magnesium, and / or acid residue (H) constituting this with a polyvalent metal other than magnesium.

The method for producing the first and second types of phosphoric acid amino acid polyvalent metal complex salts is not particularly limited as long as the dissolution properties of the obtained complex salts are insoluble in neutral to alkaline water and soluble in acidic water. Then, the following four methods can be mentioned as a preferable method.

In the first method, a precipitate obtained by dispersing and heating a second phosphate of alkaline earth metal in an aqueous solution of an excess amount of basic amino acid (basic solution is basic) is separated, and the separated precipitate is washed as necessary to prepare. Way. As a specific example, with respect to the excess amount of the concentrated aqueous solution (basic) of the free basic amino acid produced by dehydrochlorication from the salt of a basic amino acid, for example, lysine hydrochloride, by ion exchange resin treatment etc., magnesium hydrogen phosphate and calcium hydrogen phosphate And a method of adding a second phosphate of an alkaline earth metal such as stirring and stirring under heating. The alkaline earth metal diphosphate in the liquid mixture disappears over time, and the phosphoric acid amino acid alkaline earth metal complex salt is produced as a precipitate. After the precipitate is separated into solid and liquid, the separated solid phase is washed with water as necessary to remove excess basic amino acid and dried, whereby the first type of phosphate amino acid polyvalent metal complex salt is mainly obtained.

The second method is prepared by separating an precipitate obtained by mixing an aqueous solution of a suitable alkaline earth metal salt with a regular phosphoric acid in a g equivalent ratio of 2.9 to 2.0: 3.0 in an aqueous solution of an excess amount of basic amino acid, and washing the separated precipitate as necessary. That's how. As a specific example, 3 g equivalent or more of concentrated aqueous solution of basic amino acid is neutralized to 3 g equivalent of phosphoric acid to make a high concentration of a third phosphate solution, and then 2.9 to 2.0 g equivalent of an aqueous solution of a neutral salt of alkaline earth metal such as magnesium chloride or magnesium sulfate is added. After stirring and mixing, and separating the produced precipitate into solid-liquid, the method of washing excess basic amino acid with water, and drying it is mentioned.

In this method, mainly according to the addition rate of alkaline earth metal and the kind of various crystals at the time of addition, the said complex salt of the said 1st and 2nd type is obtained, respectively. That is, alkaline earth metal neutral salt solution is used in a ratio close to 2 g equivalent to 3 g equivalent of phosphoric acid, and various alkaline crystal salts of the first type are added to the third phosphate solution of basic amino acid to gradually add alkaline earth neutral salt solution. In the case of, the composite salt of the first type is mainly obtained. In contrast, when the addition amount of the alkaline earth metal neutral salt solution is rapidly added at a ratio close to 2.8 g equivalents to 3.0 g equivalents of phosphoric acid, a second type of complex salt is obtained.

In the third method, a solution obtained by mixing an aqueous solution of a basic amino acid and a fixed phosphoric acid in a neutral weight ratio of 1.0: 3.0 is added to the solution, and the mixture is neutralized by adding 2.9 to 2.0 hydroxides of alkaline earth metal in a g equivalent ratio, and the resulting precipitate is separated. The separated precipitate is washed and prepared as necessary. As a specific example, 1.0 g equivalent of the concentrated aqueous solution of basic amino acid and 3.0 g equivalent of the phosphoric acid are mixed and neutralized, and it is made into the concentrated aqueous solution of basic amino acid primary phosphate, and 2.9-2.0 g equivalent of alkali earth metal hydroxides, such as magnesium hydroxide and calcium hydroxide, is added to this solution. The method of adding and mixing as an aqueous dispersion is mentioned. The hydroxide of the added alkaline earth metal disappears over time, and a phosphoric acid amino acid alkaline earth metal complex salt is produced as a precipitate. After the precipitate is subjected to solid-liquid separation, the obtained solid phase is washed with water as necessary to remove excess basic amino acids and dried, whereby a second type of complex salt is mainly obtained.

The fourth method is a method in which a mixture is heated and dried after mixing phosphoric acid, an aqueous solution of basic amino acid and a hydroxide of an alkaline earth metal. For example, 2.9 to 2.2 hydroxides of alkaline earth metals are added and mixed to a solution in which the aqueous solution of the basic amino acid and the phosphorus acid are neutralized in a g equivalent ratio of 0.05 to 0.8: 3.0, and then the mixture is heated to dry. Way. As a more specific example, 0.05-0.8 g equivalent of basic amino acid and 3.0 g equivalent of basic phosphoric acid are mixed and neutralized to form a mixed concentrated aqueous solution of primary phosphate and regular phosphoric acid, and 2.9 to 0.8 hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide are added to the solution. The method of adding and mixing 2.2 g equivalent as an aqueous dispersion is mentioned. The hydroxide of the added alkaline earth metal disappears over time, and a phosphoric acid amino acid polyvalent metal complex salt is produced as a precipitate. Drying the precipitate as it is for each reaction mixture mainly yields a complex salt of the second type.

What is common in these four methods is the phosphoric acid amino acid polyvalent metal complex represented by the formula (1) of the present invention under conditions in which a concentrated aqueous solution of basic amino acid (basic as described above) is used as a raw material and the basic amino acid is relatively high in concentration. It is the point which reacts and produces salt. In the present invention, the concentration of the basic amino acid is, in the case of the second method in which the highest concentration is selected, the total moisture present in the reaction generation system is 100 parts by weight, and the concentration is preferably 10 to 60 parts by weight, and the lowest concentration is For the fourth method selected, a concentration of 3 to 20 parts by weight is preferred with respect to 100 parts by weight of total moisture.

In addition, these four methods can be combined suitably. As a specific example, in the reaction solution in which the phosphoric acid amino acid alkaline earth metal complex salt is formed as a precipitate in the first method, an appropriate amount of a concentrated aqueous solution of a neutral salt of phosphorous acid and alkaline earth metal is added, stirred, mixed and heated to maintain the excess amount remaining in the reaction solution. Reaction with an excess amount of basic amino acid and phosphoric acid remaining in the reaction solution by adding an appropriate amount of a hydroxide of alkaline earth metal to the reaction solution formed by reacting the basic amino acid and the phosphoric acid amino acid alkaline earth metal complex salt as a precipitate in the second method. May be enumerated. The phosphoric acid amino acid alkaline earth metal composite salt obtained here is a mixture of the first type complex salt and the second type complex salt, and these preparation methods and reaction conditions affect the composition (ratio).

The process for producing the phosphate amino acid polyvalent metal complex salts, which belong to the third and fourth types of the present invention, wherein the phosphoric acid is polyphosphoric acid and metaphosphoric acid, respectively, has a dissolution property of the obtained complex salt insoluble in neutral to alkaline water and in acidic water. It will not be restrict | limited in particular if it is soluble, and is substantially the same as the complex salt of regular phosphoric acid except that phosphoric acid is polyphosphoric acid and metaphosphoric acid, respectively. Such a manufacturing method is classified roughly and the following three methods are mentioned as a preferable method.

In the first method, an aqueous solution of a neutral salt of alkaline earth metal is phosphated to a basic aqueous solution in which the phosphoric acid (ie, polyphosphoric acid or metaphosphoric acid) and / or the alkali metal salt of the phosphoric acid is added to an aqueous solution of an excessive amount of basic amino acid (basic). 70 to 130 g equivalents per 100 g equivalents are added, the resulting precipitate is separated, and the separated precipitate is washed and dried as necessary to obtain the desired complex salt.

In the second method, 70 to 130 g equivalents of alkaline earth metal hydroxides and / or oxides are added and mixed to an acidic to neutral aqueous solution obtained by neutralizing the phosphoric acid to 2 to 50 g equivalents of an aqueous basic amino acid solution per 100 g equivalents of phosphoric acid, The precipitate produced by the reaction is separated and the separated precipitate is washed and dried as necessary to obtain the desired complex salt.

In the third method, an acidic aqueous solution obtained by neutralizing the phosphoric acid in an amount of 2 to 15 g equivalents of an aqueous basic amino acid solution per 100 g equivalents of phosphoric acid is added and mixed with 85 to 130 g equivalents of an alkaline earth metal hydroxide and / or an oxide to neutralize the reaction product. This is a method for drying the reaction mixture as it is to obtain a composition containing the desired complex salt.

The third and fourth types of the phosphoric acid amino acid polyvalent metal complex salts of the present invention may be prepared separately, but a mixture of the third and fourth types of complex salts may be prepared by simultaneously or premixing the raw material polyphosphoric acid and metaphosphoric acid. The method of obtaining is also used as a preferable method.

The complex salts of the first and second types of the present invention and the complex salts of the third and fourth types of the present invention, in addition to the method of separately preparing them, include three kinds of phosphates (i.e., phosphoric acid, polyphosphoric acid and metaphosphoric acid) as raw materials It is also possible to use a method of obtaining the first to fourth type of complex salts as a mixture thereof by appropriately or simultaneously mixing them in advance, but a reaction mixture in which a mixture of the first and second type of complex salts is formed in advance can be used. Polyphosphoric acid and / or metaphosphoric acid and alkaline earth metal salts are added to produce a third and / or fourth type of complex salt, and a fixed phosphoric acid and an alkali are added to the reaction solution in which a mixture of the third and fourth types of salt is formed in advance. A method of producing a first and / or second type of complex salt by adding an earth metal salt is used as a preferable method as a method of obtaining a mixture of complex salts of the first to fourth types.

Phosphoric acid amino acid polyvalent metal complex salt of the fifth type of the present invention, as indicated by the formula (4), as described above, for example, a basic amino acid, magnesium salt and regular phosphoric acid, the basic amino acid is relatively high concentration and neutral to alkaline Complex salts obtained as crystal precipitates when coexisting in an aqueous solution under conditions, that is, complex salts in which alkaline earth metals are limited to magnesium in the complex salts of the first or second type of the present invention represented by the above formula (hereinafter, intermediate complex Salt), which is a composite salt obtained by treating the intermediate composite salt with a divalent or trivalent polyvalent metal other than magnesium. Specific examples of such complex salts include salts based on a tertiary phosphate or tertiary phosphate of phosphorous acid and corresponding to a mixture of this and a second phosphate, and these have a basic amino acid (R) of 0.05 per mole of the phosphorous acid. To 1 mole, magnesium (Mg) is 0.85 to 1.43 moles, divalent or trivalent polyvalent (m) metal (M) other than magnesium is 0.02 to 0.6 moles, and acid residue (H) is 0 to 0.3 moles. In the formula (4), a + 2b + mc + d is 3, the second phosphate is 1/2 or less of the third phosphate in a molar ratio, and the water contained in the complex salt is 30% or less. In addition, in Formula 4, n is theoretically 0, 1 or 2, but becomes 0 to 20 depending on actual drying conditions.

Examples of the divalent or trivalent polyvalent metal other than magnesium constituting the fifth type of phosphate amino acid polyvalent metal complex salt of the present invention include alkali earth metals such as calcium, strontium and barium, transition metals such as aluminum, iron, cobalt, manganese and chromium. And other divalent metals such as zinc, cadmium, and the like, but calcium, aluminum, iron, and zinc are preferred in view of being biologically safe. These polyvalent metals are used in a suitable form such as salts, hydroxides or oxides thereof when producing the complex salt of the fifth type of the present invention.

There is no particular limitation as long as the dissolution properties of the complex salts obtained also in the process for producing the fifth type of phosphoric acid amino acid polyvalent metal complex salt of the present invention are insoluble in neutral to alkaline water and soluble in acidic water. After mixing with a solution of other divalent or trivalent polyvalent metal salts, a method of separating and drying them is preferably used. In addition, the intermediate complex salt can be produced by, for example, limiting the alkaline earth metal to magnesium in the method for producing the complex salt of the first or second type.

The divalent or trivalent polyvalent metals other than magnesium used when the intermediate complex salt is treated to prepare the fifth type of complex salt of the present invention, as described above, may be in a suitable form such as salts, hydroxides or oxides thereof. However, in the case of salts, it can be used as their solution or dispersion. The salt solution (or dispersion) is not particularly limited, but is weakly acidic to basic, and has an aqueous solution (or an aqueous dispersion) in which polyvalent metal ions other than magnesium are dissolved in an appropriate amount of 0.001 parts by weight or more per 100 parts by weight of the solution. This is preferably used. Specifically, aqueous solutions of aluminum salts such as aluminum chloride, polyaluminum chloride, aluminum sulfate, ammonium alum, potassium alum, calcium salts such as calcium chloride, calcium sulfate, calcium nitrate, aqueous solutions or aqueous dispersions of calcium hydroxide, ferrous chloride, chloride Aqueous solutions of iron salts such as ferric iron, ferrous sulfate, ferric sulfate, iron sulfate calcium and ammonium sulfate, zinc salts such as zinc chloride and zinc ammonium chloride, or aqueous solutions or aqueous dispersions of zinc hydroxide can be exemplified. have. These polyvalent metal salt solutions other than magnesium may be used alone, or two or more thereof may be mixed and used as a mixed salt solution or a complex salt solution.

In the present invention, the required amount of divalent or trivalent polyvalent metal salts other than magnesium used for treating the intermediate composite salt is the contact time of the intermediate complex salts of these polyvalent metal salts, and divalent or trivalent polyvalent metal salts other than magnesium. Phosphoric acid in the intermediate complex salt is different depending on the concentration of the solution or dispersion of the solution and the dispersion concentration of the intermediate complex salt upon contact, since most of the divalent or trivalent polyvalent metal ions other than magnesium are transferred to the desired complex salt. Preference is given to using a molar ratio of 0.02 to 0.6 per mole.

In the present invention, in order to treat the intermediate composite salt with a divalent or trivalent polyvalent metal salt other than magnesium, after preparing the intermediate composite salt in advance, it is mixed with a divalent or trivalent polyvalent metal salt solution other than magnesium and contacted. After the separation, a method of separating and drying is preferably used. At this time, the intermediate complex salt may be dried in advance and used in powder form, but after the undried one is dispersed in a divalent or trivalent polyvalent metal salt solution other than magnesium, the intermediate complex salt may be separated and dried, or the undried intermediate complex salt. For example, a method of adding and mixing calcium hydroxide as a powder or an aqueous dispersion and then drying it as it is may be used.

In the present invention, the effect of treating the intermediate complex salt with a divalent or trivalent polyvalent metal salt other than magnesium further enhances the dissolution properties insoluble in neutral to alkaline water and soluble in acidic water. In addition, insoluble in a neutral aqueous solution having a buffering capacity is also provided. This is because by treating the intermediate complex salt with a divalent or trivalent polyvalent metal salt other than magnesium, a more insoluble surface layer composed of a salt of a divalent or trivalent polyvalent metal other than phosphorous acid and magnesium is formed on the surface of the intermediate composite salt. It is considered that the result is a complex salt insoluble in the neutral buffered aqueous solution and soluble in the acidic buffered aqueous solution as a result.

The five phosphoric acid amino acid polyvalent metal complex salts of the first to fifth types may be characterized by powder X-ray diffraction analysis in addition to the composition ratios of the phosphorous acid, the basic amino acid and the alkaline earth metal. That is, when comparing powder X-ray diffraction spectra using Kα rays, the first type of composite salt shows two large peaks at about 3.6 to 4.0 degrees and 7.2 to 7.6 degrees, whereas the second type of complex salt It shows a large peak at about 5.9 to 6.9 degrees. In addition, the complex salts of the third type and the fourth type do not exhibit a clear peak, and only a slight increase in the base line is observed in the range of about 25 ° to about 35 ° at 2θ, respectively. In the complex salt of the fifth type, peaks of the complex salt of the first or second type which are intermediate complex salts are observed, respectively.

In addition, although the said five complex salts do not show solubility with respect to neutral to alkaline water, it is recognized that there exists a difference in the elution behavior of each basic amino acid component. That is, in the complex salt of the first type, only the basic amino acid component tends to elute over time while dispersed in neutral water, whereas in the complex salts of the second to fifth types, the basic salt is neutral to neutral water. Elution of the amino acid component is extremely small.

Therefore, the second to fifth types of phosphoric acid amino acid polyvalent metal complex salts are insoluble in neutral to alkaline water, even if each of the complex salts prepared as described above or a mixture thereof is used in the form of crystal powder. It is soluble in acidic water, stable in water, and can be used as a feed additive composition for aquatic animal breeding, which releases basic amino acids from the digestive organs of aquaculture animals. It goes without saying that it is also possible to prepare these types of complex salts in the form of granules of aquatic animal feed additives. Particularly, as described below, when a biologically active substance other than the basic amino acid is used together, Is common.

On the other hand, a mixture of the first type of phosphate amino acid polyvalent metal complex salt or other type of phosphate amino acid polyvalent metal complex salt having the main component thereof is a granule having a suitable particle diameter rather than using them in the form of crystal powder as it is. It is preferable to reduce the elution of the basic amino acid component to neutral to alkaline water by molding. Even in this case, the phosphate amino acid polyvalent metal complex salt of the present invention has a property of slowly releasing basic amino acid in neutral water but easily dissolving in acidic water, and the granulated molded product is not dependent on its composition. Because of its ability to dissolve in the digestive tract, it can be used as a feed additive composition for granular aquatic animal breeding which is stable in water and releases basic amino acids from the digestive tract of aquaculture animals.

When the phosphoric acid amino acid polyvalent metal complex salt of the present invention is used as a feed additive composition for aquatic animal breeding in the form of granules, it is particularly preferable that the granules have a homogeneous granule structure. In the present invention, the granule having a homogeneous structure means that there is no composition variation between the granule fragments even when the granules are broken to form granule fragments having a particle diameter of about 0.2 to 0.5 mm (millimeter). In other words, when the composition is uniform between granule fragments having a particle diameter of about 0.2 to 0.5 mm because the particle diameter of the granules is limited in the range of about 0.2 to 0.5 mm when mixing or mixing with other feed ingredients, The composition of the granule debris is also constant, and even in the case of granules produced by mixing granulation, it does not cause a great change in the elution of the basic amino acid component.

As a granulation method, if the above-mentioned homogeneity is obtained, the method generally used can be used without a restriction | limiting in particular. As a specific example, after mixing with a suitable binder, the method of granulation by granulation methods such as extrusion granulation method (granulation method), rolling granulation method, compression granulation method, melt spray granulation method, spray drying the slurry, powder together with a suitable binder A fluid bed granulation method or a method of granulating by stirring granulation method may be preferably used.

As the binder, in the case where the complex salts of the second to fifth types are mainly used as the phosphate amino acid polyvalent metal complex salt of the present invention, any one that is generally used in this field can be used without particular limitation. Specific examples include water-soluble polysaccharides such as starch, salts of carboxymethyl cellulose, alginic acid salts, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and salts of starch glycolic acid as water-soluble binders, water-soluble proteins such as casein sodium, gelatin, soy protein, Sugars such as molasses, lactose and dextrins, and synthetic polymers such as polymethacrylic acid salts, polyvinyl alcohols, polyvinyl alkaline earth metallidons, and the like, and the like, and hydrophobic binders such as shellac resin, rosin, beeswax and paraffin wax Natural waxes, higher fatty acids such as cetanol and stearic acid, metal salts of higher fatty acids, fats and oils related to animal and vegetable fats and oils and fats of hardened plants and animals, nonionic surfactants such as glycerin monostearate, acetyl cellulose, polyvinylacetate, esters Semi-synthetic resins such as rubber Can. In the case where the complex salt of the first type is mainly used, the hydrophobic binder is preferably used, and among them, the natural waxes and the fats and oils-related substances are more preferable in terms of safety.

Next, the phosphoric acid amino acid polyvalent metal complex salt represented by the formula (5) will be described.

The phosphate amino acid multivalent metal complex salt represented by the formula (5) is again listed below.

Formula 5

R _a M _b H _c H _d PO ₄ (PO ₃ ) _m nH ₂ O

In Formula 5 above,

R is a basic amino acid hydrogen cation,

M is a polyvalent metal of valence q other than magnesium, where q is 2 or 3,

a is 0.05 to 0.4,

b is 0.90 to 1.47,

c is 0.01 to 1.4,

d is 0 to 0.3,

m is 0

a + 2 × b + q × c + d = m + 3,

n is from 0 to 10.

The raw material basic amino acid at the time of manufacturing such a complex salt is the same as that of the complex salt represented by any of Formula (1-4) mentioned above. That is, as a raw material basic amino acid at the time of manufacturing the said complex salt, 1 type, or 2 or more types of mixtures chosen from natural basic amino acids, such as lysine, arginine, ornithine, basic derivatives, and basic derivatives of neutral amino acids are mentioned. Specific examples include basic derivatives such as natural basic amino acids such as lysine, arginine, ornithine, and basic amino acid-containing peptides; And basic derivatives of neutral amino acids such as amides and esters of amino acids such as methionine, tryptophan, threonine and the like. Among these, lysine and arginine are particularly preferably used because they are excellent in terms of nutritional value, economy and solubility of salts as essential amino acids.

The complex salt of the formula (5) is, for example, a complex salt of the formula (1) wherein M is Mg, that is, a magnesium phosphate complex salt (also referred to as intermediate complex salt or Mg) represented by the following formula (6), other than magnesium in an aqueous solvent It can be produced by contacting a polyvalent metal material having a valence of 2 or 3 with a condensed phosphoric acid component (alone) or a condensed phosphoric acid component and a regular phosphoric acid component (combination).

[Formula 6]

R _a M _b H _c PO ₄ (PO ₃ ) _m nH ₂ O

In Formula 6 above,

R is a basic amino acid hydrogen cation,

a is 0.05 to 1.0,

b is 1.0 to 1.47,

c is 0 to 0.3,

a + 2b + c = 3,

n is from 0 to 10.

The Mg salt is obtained as a crystal precipitate when the basic amino acid, magnesium component and phosphoric acid component coexist in an aqueous solution under neutral to alkaline conditions where the basic amino acid is relatively high in concentration. As an example of specific preparation, Mg salt, an intermediate complex salt, is produced by adding and mixing phosphoric acid with magnesium hydroxide and / or magnesium oxide in a molar ratio of 1: 0.85 to 1.43 in an aqueous solution of an excess amount of basic amino acid (basic), followed by heating and stirring. do. Mg salt can be separated and obtained from such a reaction liquid by solid-liquid separation operation, such as filtration.

In the present invention, as a divalent or trivalent polyvalent metal material other than magnesium used when treating Mg salt, alkaline earth metals such as calcium, strontium, barium, aluminum, iron, cobalt as in the case of the complex salt of Formula 4 described above Transition metals such as manganese and chromium, and other divalent metals such as zinc and cadmium. However, calcium, aluminum, iron, and zinc are preferable because they are biologically safe. These polyvalent metals are used in a suitable form such as salts, hydroxides or oxides thereof when preparing the complex salt of the formula (5). Specifically, aluminum salts such as aluminum chloride, polyaluminum chloride, aluminum sulfate, ammonium alum, potassium alum, calcium salts such as calcium chloride, calcium sulfate, calcium nitrate, or calcium hydroxide, ferrous chloride, ferric chloride, sulfuric acid Iron salts, such as ferrous iron, ferric sulfate, calcium sulfate, ferrous ammonium, zinc salts, such as zinc chloride and zinc ammonium chloride, or zinc hydroxide, can be illustrated. These polyvalent metal salts may be used alone, but may be used as a mixed salt of a solid phase by mixing two or more kinds thereof, or as a solution or a complex salt solution thereof.

In the present invention, condensed phosphoric acid components used in the contact treatment of Mg salts include pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and other polyphosphoric acids, or salts thereof, trimethacrylic acid, tetramethic acid, hexamethic acid and Other metaphosphoric acids or salts thereof are used, and as the phosphorus acid component, phosphorous acid or a salt thereof is used. As the salt, metal salts such as sodium, potassium, magnesium, calcium, iron, zinc, aluminum and ammonium salts can be exemplified. In particular, when a divalent or trivalent metal salt such as calcium salt or iron salt is used, the polyvalent metal material is also contained at the same time, and the amount of the polyvalent metal material can be reduced. These condensed phosphoric acid components and regular phosphoric acid components may be used alone, respectively, or may be used by mixing two or more kinds. In addition, they may be used as they are, regardless of whether they are solid or liquid, but they may also be used as aqueous solutions.

In the present invention, the necessary amount of the divalent or trivalent polyvalent metal material and the condensed phosphoric acid component (and the proper phosphoric acid component suitably used) used to treat the Mg salt needs to be determined in consideration of the following two points. In other words, although the contact time with the Mg salt and the dispersion concentration of the Mg salt at the time of contact are different, almost all of the polyvalent metal ions and the condensed phosphate component (and the proper phosphoric acid component suitably used) from the polyvalent metal material are of the formula (5). The transition to the final complex salts and in general, these polyvalent metals and condensed phosphate components (and proper phosphoric acid components suitably used) increased the amount of the basic amino acid required for feed, while the solubility of the final complex salts is suppressed. There are two points of deterioration. Therefore, in order to maintain the expression of the effect of lowering the solubility and to maintain the content of basic amino acid, any of them can be used in a ratio of 0.004 to 1.2 in a molar ratio with respect to 1 mol of phosphoric acid in the Mg salt, preferably in a ratio of 0.01 to 0.5.

The three types of contact between the Mg salt (intermediate complex salt) and the polyvalent metal material and the condensed phosphoric acid component or the condensed phosphoric acid component and the regular phosphoric acid component are usually performed in an aqueous solvent. Generally, it carries out by stirring-mixing Mg salt, a polyvalent metal substance, a condensed phosphoric acid component, or a condensed phosphoric acid component, and a regular phosphoric acid component in an aqueous solvent.

The Mg salt (intermediate complex salt) used herein may be, for example, a compound obtained by reacting phosphate, magnesium hydroxide, and basic amino acid, and isolating and drying from the reaction solution, but it is not necessary to isolate the Mg salt. The reaction solution can be treated as it is with condensed phosphoric acid, a properly used phosphorus acid component and a divalent or trivalent polyvalent metal material. In addition, the wet-crystal-separated wet crystal does not necessarily need to dry, but also it mixes a polyvalent metal substance, a condensed phosphoric acid component, a condensed phosphoric acid component, and the regular phosphoric acid component used suitably, and the desired polyvalent metal complex salt (final complex salt) is obtained. It can manufacture.

What is important in the mixing operation for these three types of contact is that it should be able to operate under the conditions which can always maintain neutrality or alkalinity. This is because the Mg salt, which is one of the raw materials, and the polyvalent metal complex salt, which is one of the target materials, are stable in the neutral to alkaline region but are relatively unstable under acidic conditions and are easily decomposed and dissolved. For example, in the case of using polyphosphoric acid as the condensed phosphoric acid component and calcium hydroxide as the polyvalent metal material, the Mg salt is included, rather than adding Mg salt to an aqueous solution of acidic polyphosphoric acid followed by alkaline calcium hydroxide. It is good to add calcium hydroxide and polyphosphoric acid in order to the slurry to make. It is also recommended to simultaneously add polyphosphoric acid and calcium hydroxide while maintaining the pH of the slurry containing Mg salt at 6 or higher, preferably 7 or higher. However, if exposed to acidic conditions in a very short time, there is no significant adverse effect.

In addition, when a relatively low solubility substance such as calcium hydroxide is used as the polyvalent metal substance, it may be incorporated into the target polyvalent metal complex salt (final complex salt) in an unreacted state depending on the reaction conditions, but in seawater or fresh water The effect on stability and solubility in the digestive system of aquatic animals is not particularly problematic.

There is no restriction | limiting in particular as temperature at the time of mixing and contacting these three types, It can carry out in 0-80 degreeC. If the reaction composition concentration at the time of mixing is uniformly mixed, there is no particular limitation, and it can be usually performed at a concentration of 5 to 40% as the Mg salt.

After completion of the mixing of the three components, the mixture may be immediately attached to the solid-liquid separation operation, but in order to complete the reaction, stirring is preferably performed for about 30 minutes to 1 day.

After the contact (mixing) operation, the wet crystal of the polyvalent metal complex salt obtained by solid-liquid separation such as filtration and vibration separation usually has a water content of 40 to 80%. When it dries, although it changes also according to the conditions, it has a water content of about 0 to 15% normally.

In the present invention, the effect of treating the Mg salt with a divalent or trivalent polyvalent metal material other than the condensed phosphoric acid component (and a properly used phosphorus acid component) and the magnesium component is insoluble in neutral to alkaline water of the Mg salt. It is intended to further enhance the dissolution properties soluble in acidic water and to insoluble in neutral aqueous solution having a buffering capacity. That is, by treating the Mg salt with a polyvalent metal material and a condensed phosphoric acid component (and appropriate phosphoric acid as appropriate), the polyvalent metal cation forms a more insoluble surface layer of condensed phosphoric and / or phosphorous acid and also a polyvalent metal salt on the surface of the Mg salt. It is considered that a part of crosslinks the condensed phosphate component and / or the phosphate component in the Mg salt with the surface layer portion by substituting with a basic amino acid hydrogen cation in the Mg salt. As a result, the desired final composite salt is formed which is insoluble in the neutral buffered aqueous solution and soluble in the acidic buffered aqueous solution.

Phosphoric acid amino acid polyvalent metal complex salt represented by the formula (5) of the present invention is extremely insoluble in neutral to alkaline water and dissolving in acidic water, and is extremely stable in seawater or fresh water and is also acidic. It completely dissolves in the digestive tract of aquatic animals, releasing and absorbing basic amino acids. In other words, the complex salt can be used as a feed additive composition for aquatic animal breeding, which can be digested and absorbed in the digestive organ of aquatic animals by protecting the basic amino acid, which is an effective ingredient thereof, in the water. In addition, it is needless to say that the complex salt can not only be used as a crystal powder but also formed into granules having a suitable particle diameter and can be used as a feed additive composition for aquatic animal breeding. When using a biologically active substance together, it is common to manufacture in the form of granules.

In the present invention, the granules of the phosphate amino acid polyvalent metal complex salt are more preferably selected to have a homogeneous granule structure. In the present invention, the granule having a homogeneous structure means that even when granulated fragments having a particle diameter of about one tenth to one tenth of the particle diameter are formed by crushing the original granules, It is said that there is little change. In other words, when granules are mixed with other feed ingredients or granulated, granules do not cause a significant change in the elution of the basic amino acid component even after the granules are fragmented.

The granulation method is the same as in the case of the complex salt represented by any of the above-described formulas (1) to (4). That is, as a method of granulation, if the above-mentioned homogeneity is obtained, the method generally used can be used without particular limitation. As a specific example, after mixing with a suitable binder, the method of granulation by granulation, such as extrusion granulation, rolling granulation, compression granulation, melt spray granulation, spray drying the slurry, fluid bed granulation with a suitable binder or stirring A method of assembling by an assembly method and the like can be preferably used.

The binder is also the same as in the case of the complex salts of the second to fifth types described above. That is, what is generally used as a binder can be used especially without a restriction | limiting. Specific examples of the water-soluble binder include water-soluble polysaccharides such as starch, salts of carboxymethyl cellulose, alginic acid salts, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and salts of starch glycolic acid, water-soluble proteins such as casein sodium, gelatin, and soy protein. Sugars such as molasses, lactose and dextrins, synthetic polymers such as polymethacrylate, polyvinyl alcohol and polyvinyl alkali earth metal lidone, and the like can be cited. Higher fatty acids such as waxes, cetanol, stearic acid, metal salts of higher fatty acids, animal fats and oils, hardened animal fats and oils, nonionic surfactants such as glycerin monostearate, acetyl cellulose, polyvinyl acetate, ester rubber And semisynthetic resins such as coumarone resins and synthetic polymers. .

In the phosphate amino acid polyvalent metal complex salt represented by any of the above Formulas 1 to 5 of the present invention, the ratio of the phosphate amino acid polyvalent metal complex salt and the binder when preparing this into granules varies depending on the type of the binder, The amount of 0.1 to 50 parts by weight per part also achieves the desired purpose, which is sufficient for molding holding. In addition, the particle diameter of the granules is not particularly limited, but granules having an average particle diameter of 5 mm or less are preferable in that the variation in feeding is small, and granules having an average particle diameter of 2 to 0.2 mm are different feeds. It is especially preferable at the point that mixing operation with a component becomes easy.

According to the present invention, the granules containing the phosphate amino acid polyvalent metal complex salt as an active ingredient include the purpose of adjusting the specific gravity, enhancing the strength of granules, reinforcing the inusability in the digestive organs of aquaculture aquaculture or improving the processability in producing the granules. In addition, it can also be prepared by adding other additives in addition to the complex salt and the binder. Such additives may be selected from powder or waxy materials to form homogeneous granules. Specific examples include inorganic substances such as carbonates, phosphates or hydroxides of alkaline earth metals, talc, bentonite, clay, and fine silica, or organic substances such as paraffin wax, polyethylene powder, pulp powder, cellulose powder, and chitosan.

Further, according to the present invention, granules containing the phosphate amino acid polyvalent metal complex salt as an active ingredient do not impair the protection of the complex salt in water (in fresh water or sea water) and the elution in the digestive organs of the aquaculture animal. It can be prepared by homogeneously dispersing other biologically active substances to the extent that they do not.

Examples of the biologically active substance include one kind or a mixture of two or more kinds of known nutrients and drugs such as amino acids and derivatives thereof, hydroxy cognates of amino acids, vitamins, and aquatic drug. have. Specifically, Amino acids, such as methionine, tryptophan, threonine; Amino acid derivatives such as calcium salt of N-acylamino acid and N-hydroxymethylmethionine; Hydroxy cognate compounds of amino acids such as 2-hydroxy-4-methylmercaptobutyric acid and salts thereof; Starch, fatty acid, fatty acid metal salt as a calorie source; Vitamin A, vitamin A acetate, vitamin A palmitate, vitamin B group, thiamine, thiamine hydrochloride, riboflavin, nicotinic acid, nicotinic acid amide, calcium pantothenate, cholinethenic acid choline, pyridoxine chloride, choline chloride, cyanocobalamin, biotin, folic acid, p- Vitamins such as aminobenzoic acid, vitamin D ₂ , vitamin D ₃ and vitamin E and substances having similar functions; Tetracycline, amino glycoside, macrolide, and polyether antibiotics; Sulfases such as sulfamomonotoxin and sulfadimethoxine; Antibacterial agents such as flazolidone and vanazone; Insect repellents such as negphone and pitchol and piperadine; Hormones such as estrogen, stilfestol, hexestol, tyroptin, high estrogen and growth hormone can be used.

Example

Although an Example and a comparative example demonstrate this invention in detail below, the scope of the present invention is not limited to these Examples.

In addition, in the test and the Example, the content and elution amount of amino acid as a biologically active substance were analyzed by liquid chromatography.

And the test of the elution property and protection property of a basic amino acid is performed by the method of following (a)-(c) about Examples 1-24, and the following (d)-(f) of Examples 25-38. Done by the method.

(a) elution in pure water:

1.00 g of the prepared sample was added to a 200 ml Erlenmeyer flask, 100 ml of pure water was injected, sonicated at room temperature for 10 minutes, filtered, and the amount of basic amino acid (eluted from the sample) in the filtrate was analyzed. Sex was evaluated by dissolution rate.

The dissolution rate was calculated by the following equation.

[Equation 1]

Dissolution rate (= elution) (%) = A / B x 100 (%)

A: amount of basic amino acid eluted

B: Basic amino acid amount in the used sample

(b) protection in seawater:

0.5 g of the prepared sample was put into a 300 ml Erlenmeyer flask, and 200 ml of artificial seawater shown in Table 1 was injected and vibrated at 25 ° C. for 2 hours. After the vibration was completed, the amount of basic amino acid eluted was analyzed, and the ratio of the amount of the basic amino acid residue to the amount of basic amino acid in the sample used was calculated by the following equation (2) to make the protection in seawater.

TABLE 1

Artificial seawater

[Equation 2]

Protection (%) = ((B-A) / B) 100 (%)

A and B are the same as in Formula (iii).

Therefore, (B-A) becomes a cuprous basic amino acid.

(c) elution in the digestive system of aquatic animals:

About 0.5 g of the prepared sample was put into a 300 ml Erlenmeyer flask, and 200 ml of acetic acid-phosphate buffer (A solution) shown in Table 2 corresponding to the digestive tract liquid of aquatic animals was injected and vibrated at a temperature of 25 ° C. for 2 hours. . After the vibration was completed, the elution amount of the basic amino acid was analyzed, and the ratio between the amount of the basic amino acid eluted and the amount of the basic amino acid in the sample used was calculated by Equation 1 to obtain elution in the digestive organs of the marine animal.

TABLE 2

Acetic Acid-Phosphate Buffer (A Solution)

(d) elution in pure water:

0.1 g of the prepared sample was placed in a 50 ml volumetric flask, 50 ml of pure water was added thereto, sonicated at room temperature for 10 minutes, filtered, the amount of basic amino acid in the filtrate was analyzed, and elution in pure water was evaluated as the dissolution rate. The dissolution rate was calculated by the above equation (1).

(e) Protection in seawater:

0.1 g of the prepared sample was placed in a 50 ml volumetric flask, 50 ml of seawater was added, sonicated at room temperature for 10 minutes, filtered, the amount of basic amino acid in the filtrate was analyzed, and the elution to seawater was evaluated as the elution rate. Seawater was used by dissolving a commercial salt for commercial seawater in pure water at a predetermined concentration (Table 1 above).

The dissolution rate was calculated by the above equation (1). Multiplying this result by 100 is protection.

(f) Elution in equivalent amounts of aquatic digestive system:

About 0.25 g of the prepared sample was put into a 300 ml Erlenmeyer flask, and 50 ml of acetic acid-phosphate buffer (B solution) shown in Table 3 was added as a model of aquatic animal digestive fluid, and vibrated at a temperature of 25 ° C for 2 hours. After the vibration was completed, the resultant was filtered, the amount of basic amino acids in the filtrate was analyzed, and the elution property in the equivalent of the digestive fluid of the fishery organ was calculated by the above formula (1).

TABLE 3

Acetic Acid-Phosphate Buffer (B Solution)

Example 1

To 1,300 g of L-lysine aqueous solution (concentration: 45% by weight), 174.3 g of dibasic magnesium phosphate trihydrate was added and stirred with heating at 80 ° C. for 3 hours. As a result, granular crystals of dibasic magnesium phosphate trihydrate were obtained. It disappeared and produced a large amount of fine crystals. The resulting crystals were collected by filtration, washed with 1,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 285 g of white crystal powder.

As a result of adding 1 g of this white powder to 100 ml of pure water and artificial seawater, respectively, and stirring and observing, dissolution (apparent change in sample shape) was not recognized.

Example 2

To a solution neutralized by mixing 4386 g of an aqueous L-lysine solution (concentration: 20% by weight) and 231 g of phosphorous acid (concentration: 85%), a solution in which 493 g of magnesium sulfate heptahydrate was dissolved in 1,000 ml of water was added at once. The resulting gelled precipitate was collected by filtration, washed with 12,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 280 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized.

Example 3

To a solution neutralized by mixing 650 g of L-lysine aqueous solution (concentration: 45% by weight) and 461.2 g of fixed phosphoric acid (concentration: 85%), a mixture of 291.7 g of magnesium hydroxide dispersed well in 1,000 ml of water was added and mixed. The reaction was exothermic and the whole became a white solid. After heating this white solid at 95 degreeC for 3 hours, 3,000 ml of pure waters were added, it grind | pulverized well, solids were collected by filtration, washed with 3,000 ml of water, and it dried under reduced pressure at 60 degreeC, and 750 g of white powders were obtained.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized.

Example 4

311 g of an aqueous L-lysine solution (concentration: 47% by weight) and 461.2 g of fixed phosphoric acid (concentration: 85%) were neutralized, and a dispersion obtained by uniformly dispersing 291.7 g of magnesium hydroxide in 700 ml of water was reacted. Exothermic and turned to a white solid. After heating this white solid at 90 degreeC for 3 hours, it was crushed and dried under reduced pressure at 60 degreeC, and 750g of white powder was obtained.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized.

Example 5

To the solution neutralized by mixing 4386 g of aqueous L-lysine solution (concentration: 20% by weight) and 231 g of phosphorous acid (concentration: 85%), 20 g of the white crystal powder obtained in Example 1 was added, followed by 407 g of magnesium chloride hexahydrate. A small amount of the solution dissolved in 500 ml of water was slowly added to form fine crystals. The resulting crystals were collected by filtration, washed with 3,000 ml of water, and dried under reduced pressure at 60 ° C. to give 573 g of white crystal powder.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized.

Example 6

87.2 g of trihydrate of dibasic magnesium phosphate was added to 730 g of an aqueous L-lysine solution (concentration: 40% by weight), and stirred at 80 ° C for 3 hours. As a result, granular crystals of trihydrate of dibasic magnesium phosphate were lost. Fine crystals were produced. After adding 46.1 g of phosphorous acid (concentration: 85%) to the mixture slowly while cooling, a solution obtained by dissolving 98.6 g of magnesium sulfate heptahydrate in 150 ml of water was added all at once, resulting in a viscous crystal slurry. From this, the crystals were obtained by filtration, washed with 1,300 ml of water, and then dried under reduced pressure at 60 ° C to obtain 198 g of white crystal powder.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized.

Example 7

To a solution neutralized by mixing 4,873 g of L-lysine aqueous solution (concentration: 30% by weight) and 461 g of phosphorous acid (concentration: 85%), a solution obtained by dissolving 610 g of magnesium chloride hexahydrate in 1,000 ml of water was added at once. The resultant viscous mixture and a dispersion of 93.3 g of magnesium hydroxide well dispersed in 700 ml of water were uniformly mixed and allowed to stand overnight, resulting in a white precipitate. The precipitate was collected by filtration, washed with 7,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 980 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized.

Example 8

For the crystalline powder and the white powder obtained in Examples 1 to 7, the water content by the Kahl Fischer method and the dry weight loss method (120 ° C., vacuum, 3 hours), the lysine content by liquid chromatography, ICP (inductively coupled plasma) Mg content and lysine content were analyzed by luminescence analysis. The results are shown in Table 4 below. In addition, the lysine content melt | dissolved the sample in diluted hydrochloric acid, and analyzed by liquid chromatography. In addition, elution in pure water, protection in seawater, and elution in the digestive tract of aquatic animals are shown in Table 4.

TABLE 4

Composition Analysis and Elution Characteristics of Amino Acid Complex Salt (Unit: wt%, [], Phosphoric Acid Equivalent Ratio)

Example 9

A solution was neutralized by mixing 650 g of L-lysine aqueous solution (concentration: 45% by weight) and 461.2 g of regular phosphoric acid (concentration: 85%), and a dispersion obtained by dispersing 201.5 g of magnesium oxide in 600 ml of water. The whole was a white solid. The white solid was crushed, washed with 12,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 650 g of white powder.

The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of diluted hydrochloric acid was measured, and found to be 112 mg / dl, and the L-lysine content was 11.2%. Further, 1.00 g of this white powder was added to 100 ml of pure water and sonicated for 5 minutes, and the concentration of L-lysine in the supernatant was measured to be 12 mg / dl, and the elution in pure water was 10.7%. As a result of evaluating the protection of the white powder in the seawater and the elution in the digestive tract liquid of the aquatic animal, the protection in the seawater was 88%, and the elution of the aquatic animal in the digestive tract liquid was 100%.

Example 10

311 g of an aqueous L-lysine solution (concentration: 47% by weight) and 461.2 g of fixed phosphoric acid (concentration: 85%) were neutralized, and a dispersion solution of 233.3 g of magnesium hydroxide and 74.1 g of calcium hydroxide dispersed in 700 ml of water was uniformly mixed. The reaction was exothermic to cause the whole to become a white solid. The white solid was crushed, washed with 10,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 600 g of white powder.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized. The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of dilute hydrochloric acid was measured, and the result was 65 mg / dl and the L-lysine content was 6.5%. Further, 1.00 g of this white powder was added to 100 ml of pure water, mixed and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 24 mg / dl, and the dissolution rate in pure water was 36.9%. As a result of evaluating the protection of the white powder in seawater and the elution in the digestive tract of aquatic animals, the protection in the seawater was 62%, and the elution of the aquatic animals in the digestive tract was 100%.

Example 11

A solution obtained by dissolving 294.4 g of calcium chloride dihydrate in 300 ml of water was added to a solution in which 4,386 g of L-lysine aqueous solution (concentration: 20% by weight) and 203.9 g of sodium hexametaphosphate were mixed. The resulting gel precipitate was collected by filtration, washed with 2,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 238 g of white powder.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized. L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of dilute hydrochloric acid was measured, and as a result, it was 125 mg / dl, and the L-lysine content was 12.5%. Furthermore, 1.00 g of this white powder was added and mixed with 100 ml of pure water and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 7 mg / dl, and the dissolution rate in pure water was 5.6%. As a result of evaluating the protection of the white powder in the seawater and the elution in the digestive tract solution of the aquatic animal, the protection in the seawater was 93%, and the elution of the aquatic animal in the digestive tract fluid was 100%.

Example 12

To a solution in which 466.6 g of L-lysine aqueous solution (concentration: 47% by weight) and 183.9 g of sodium tripolyphosphate were dissolved in 1,000 ml of water, a dispersion in which 9.26 g of calcium hydroxide and 147.2 g of calcium chloride dihydrate were dispersed and dissolved in 300 ml of water was added. The resulting gelled precipitate was collected by filtration, washed with 12,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 180 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and seawater, respectively, and observed by stirring, and dissolution was not recognized. The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 dilute hydrochloric acid was measured, and the result was 98 mg / dl, and the L-lysine content was 9.8%. Furthermore, 1.00 g of this white powder was added and mixed with 100 ml of pure water and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 8 mg / dl, and the elution in pure water was 8.1%. As a result of evaluating the protection of the white powder in the seawater and the elution of the aquatic animal in the digestive tract solution, the protection in the seawater was 91%, and the elution of the aquatic animal in the digestive tract fluid was 100%.

Example 13

To a solution obtained by mixing and neutralizing 337.9 g of tetrapolyphosphoric acid (H6P4O13) with 609 g of an aqueous L-lysine solution (concentration: 30% by weight), a dispersion obtained by dispersing 259.3 g of calcium hydroxide in 500 ml of water was added. The mixture solidified entirely upon exotherm. The solid was pulverized, washed with 12,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 505.9 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and seawater, respectively, and observed by stirring, and dissolution was not recognized. The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of diluted hydrochloric acid was measured, and found to be 165 mg / dl and the L-lysine content was 16.5%. Further, 1.00 g of this white powder was added and mixed to 100 ml of pure water and sonicated for 5 minutes, and then the concentration of L-lysine in the supernatant was 18 mg / dl. The elution in pure water was 11%. As a result of evaluating the protection of the white powder in seawater and the elution of the aquatic animal to the digestive tract liquid, the protection in the seawater was 87%, and the elution of the aquatic animal in the digestive tract liquid was 100%.

Example 14

487 g of an aqueous L-lysine solution (concentration: 30% by weight) was mixed with 51.9 g of calcium hydroxide and 216 g of calcium dihydrogen phosphate (CaH 2 P 2 O 7) and heated to 90 ° C. while stirring, and the mixture gradually solidified. The solid was triturated, washed with 10,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 356 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and seawater, respectively, and observed by stirring, and dissolution was not recognized. The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of dilute hydrochloric acid was measured, and found to be 116 mg / dl and the L-lysine content was 11.6%. Further, 1.00 g of this white powder was added to 100 ml of pure water, mixed and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 27 mg / dl, and the dissolution rate in pure water was 23%. As a result of evaluating the protection of the white powder in the seawater and the elution in the digestive tract solution of the aquatic animal, the protection in the seawater was 76%, and the elution of the aquatic animal in the digestive tract fluid was 100%.

Example 15

To 292 g of an aqueous L-lysine solution (concentration: 50% by weight), 337.9 g of tetrapolyphosphoric acid (H6P4O13) and 150 g of water were mixed with cooling to neutralize a dispersion in which 259.3 g of calcium hydroxide was dispersed in 400 ml of water. The mixture solidified entirely upon exotherm. This solid was pulverized and dried under reduced pressure at 60 ° C. to obtain 690 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and seawater, respectively, and observed by stirring, and dissolution was not recognized. L-lysine concentration of the solution which melt | dissolved 1.00 g of this white powder in 100 ml of diluted hydrochloric acid was measured, and it was 212 mg / dl, and the L-lysine content was 21.2%. Further, 1.00 g of this white powder was added and mixed to 100 ml of pure water and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 76 mg / dl, and the dissolution rate in pure water was 36%. As a result of evaluating the protection of the white powder in the seawater and the elution of the aquatic animal in the digestive tract solution, the protection in the seawater was 62%, and the elution of the aquatic animal in the digestive tract fluid was 100%.

Example 16

A solution obtained by dispersing 337.9 g of tetrapolyphosphoric acid (H6P4O13) and 260 ml of pure water in 363 g of an aqueous solution of L-lysine (concentration: 50% by weight) while cooling was added to a neutralized solution. did. The mixture solidified entirely upon exotherm. The solid was pulverized, washed with 12,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 165 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and seawater, respectively, and observed by stirring, and dissolution was not recognized. The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of diluted hydrochloric acid was measured, and found to be 126 mg / dl, and the L-lysine content was 12.6%. Further, 1.00 g of this white powder was added to 100 ml of pure water, mixed and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 2.6 mg / dl, and the dissolution rate in pure water was 2.1%. As a result of evaluating the protection of the white powder in the seawater and the elution in the digestive tract liquid of the marine animals, the protection in the seawater was 97%, and the elution of the marine animal in the digestive tract liquid was 100%.

Example 17

To 363 g of an aqueous L-lysine solution (concentration: 50% by weight), 467 g of metaphosphoric acid ((HPO ₃ ) _n ) and 200 ml of pure water were mixed with cooling to neutralize a dispersion in which 166.7 g of calcium hydroxide was dispersed in 300 ml of water. The mixture solidified entirely upon exotherm. The solid was pulverized, washed with 12,000 ml of water, and dried under reduced pressure at 60 ° C. to obtain 295 g of a white powder.

1 g of this white powder was added to 100 ml of pure water and seawater, respectively, and observed by stirring, and dissolution was not recognized. The L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of diluted hydrochloric acid was measured, and found to be 99 mg / dl, and the L-lysine content was 9.9%. Further, 1.00 g of this white powder was added to 100 ml of pure water, mixed and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 2.4 mg / dl, and the dissolution rate in pure water was 2.4%. As a result of evaluating the protection of the white powder in the seawater and the elution in the digestive tract solution of the aquatic animal, the protection in the seawater was 97%, and the elution of the aquatic animal in the digestive tract fluid was 100%.

Example 18

For the crystalline powder and the white powder (intermediate complex salt to the complex salt represented by the formula 4) obtained in Examples 1 to 4, 250 g each was mixed with 40 g of calcium chloride dihydrate and 2,000 ml of water, followed by room temperature for 2 hours. Stirred at. Solid content was separated from this liquid mixture by filtration, and it dried and obtained 253-241g of four types of calcium-treated complex salts 1-4 of the general formula (4).

Example 19

For the crystal powders (intermediate complex salts) obtained in Examples 5 and 6, 100 g each of 20 g of zinc chloride was mixed with 1,000 ml of water and stirred at room temperature for 3 hours. Solid content was isolate | separated from this liquid mixture, and it dried, and 103g of two types of the zinc treatment complex salts V and VI of 2 types respectively obtained were obtained.

Example 20

100 g of the white powder (middle complex salt) obtained in Example 7 was mixed with 1,000 ml of water, and 30 g of ammonium aluminum sulfate (plaque) was added thereto, followed by stirring at room temperature for 23 hours. Solid content was isolate | separated from this liquid mixture, and it dried, and 101g of target aluminum treatment composite salt (K) was obtained.

Example 21

For the crystalline powder and the white powder obtained in Examples 1 to 7 and the treated complex salts I to VIII obtained in Examples 18 to 20, the water content by the Kahl Fischer method and the drying loss method (120 ° C., vacuum, 3 hours) , Lysine content by liquid chromatography, Mg content and phosphorus content by ICP (inductively coupled plasma) emission spectrometry were analyzed. The results are shown in Table 5 below. In addition, the lysine content was analyzed by liquid chromatography by dissolving the sample in dilute hydrochloric acid. Moreover, the elution property in pure water, the protection property in seawater, and the elution property in a digestive liquid were shown in Table 5 together.

TABLE 5

Composition Analysis and Dissolution Characteristics of Amino Acid Complex Salt [Unit: wt%]

Example 22

A solution of 174.2 g of L-arginine and 98.0 g of phosphorous acid (concentration: 85%) in 300 ml of water was mixed with a dispersion of 72.9 g of magnesium hydroxide well dispersed in 200 ml of water. It became. After heating this white solid at 95 degreeC for 3 hours, 1,000 ml of pure waters were added, it was crushed well, solids were collected by filtration, washed with 1,000 ml of water, and it dried under reduced pressure at 60 degreeC, and obtained 235 g of white powders.

1 g of this white powder was added to 100 ml of pure water and artificial seawater, respectively, and observed by stirring, and dissolution was not recognized. L-lysine concentration of the solution of 1.00 g of this white powder dissolved in 100 ml of dilute hydrochloric acid was measured, and found to be 370 mg / dl and an L-lysine content of 37.0%. Furthermore, 1.00 g of this white powder was added and mixed with 100 ml of pure water and sonicated for 5 minutes, and then the L-lysine concentration of the supernatant was measured to be 100 mg / dl, and the dissolution rate in pure water was 27.0%. As a result of evaluating the protection of the white powder in the seawater and the elution in the digestive tract liquid of the marine animals, the protection in the seawater was 50%, and the elution of the marine animal in the digestive tract liquid was 100%.

Example 23 (Feed additive composition (1) for aquatic animal breeding).

200 g of the white crystalline powder obtained in Example 1 was mixed with 150 g of hardened soybean oil, and then extruded from a die having a diameter of 1 mm at 65 ° C. using a heating extruder, finely cut to a length of about 1 mm, and formed into granules having a particle diameter of about 1 mm. did.

The obtained granules were evaluated for protection in seawater and elution in digestive tract fluids of aquatic animals, and as a result, the protection in seawater was 55%, and the elution in fisheries gut 95%.

Example 24 (Feed Additives for Aquatic Animal Breeding (2))

300 g of the white powder obtained in Example 3, 20 g of methionine powder, 50 g of calcium carbonate, 30 g of casein sodium and 5 g of starch glycol sodium were mixed and kneaded by adding 100 ml of water thereto, followed by extrusion using a disk pelletizer having a diameter of 2 mm. It was cut finely to a length of about 2 mm, dried, and molded into granules having a particle diameter of about 2 mm.

The obtained granules were divided into small pieces having a particle diameter of about 0.5 mm in the cutter, and extruded by heating in dilute hydrochloric acid for each of the five particles, and the amino acid content was measured. As a result, the difference in amino acid content between each small piece was determined. I couldn't find it. The obtained granules were evaluated for their elution in the digestive tract fluid of aquatic animals, and their protection in seawater was 97% for lysine and 64% for methionine. And methionine were 95%. In addition, the same evaluation was performed on the small pieces having a particle diameter of about 0.5 mm, and the protection in seawater was 95% for lysine and 62% for methionine, and elution in digestive tract fluid was 98% for both lysine and methionine. It was.

In the following examples, the contents of phosphorus and metal components were evaluated by ICP (inductively coupled plasma) emission spectrometry, and moisture was evaluated by dry weight loss method (135 ° C., 30 minutes).

Example 25

A dispersion of 1.55 Kg of L-lysine aqueous solution (concentration: 50% by weight) and 0.86 Kg of magnesium hydroxide dispersed in 3.2 L of water and 2.99 Kg of 37% phosphorous acid were mixed and heated and stirred at 80 ° C. for 3 hours, followed by adding 20 L of water. . To the obtained reaction mixture, a dispersion obtained by dispersing 17.9 Kg of an aqueous 50% L-lysine solution and 9.84 Kg of magnesium hydroxide in 36.8 L of water and 34 Kg of 37% phosphorous acid was simultaneously added over 90 minutes. In the meantime, the temperature of the reaction liquid was kept at 69-72 degreeC. In addition, the pH ranged from 8.2 to 8.5. 53 Kg of 128 Kg of the obtained slurry was vibrated and the obtained crystals were washed with 36 L of water. The wet crystals were dried in an air stream at 80 ° C. to obtain 11.4 Kg of dry magnesium salt crystals (medium complex salt).

The contents of lysine, Mg and PO ₄ in this crystal were 20.0%, 18.9% and 51.1%, respectively. In addition, the elution of the crystals in seawater, pure water, and aquatic gut fluid was 19%, 17%, and 100%, respectively.

Example 26

7.0 g of tripolyphosphoric acid was dissolved in 500 ml of water, 40 g of the Mg salt obtained in Example 25 and 8.75 g of calcium hydroxide were added in this order, stirred at room temperature for 1 hour, and then filtered by suction filtration. The obtained wet crystals were dried under reduced pressure at 65 ° C. to obtain 42.0 g of crystals (final complex salt).

The contents of lysine, Mg, P and Ca in the present crystal were 11.8%, 13.1%, 16.6% and 8.4%, respectively, and the water content was 11.5%. In addition, the elution of the crystals in seawater, pure water, and aquatic digestive system equivalents was 2%, 2%, and 100%, respectively.

Comparative Example 1

41.2 g of dry crystals were obtained as in Example 26 except that tripolyphosphoric acid was not used.

The elution of this crystal in the equivalents of seawater, pure water, and aquatic digestive systems was 9%, 7%, and 100%, respectively.

Example 27

38.6 g of dry crystals (final complex salt) were obtained as in Example 26, except that 2.6 g of tripolyphosphoric acid and 1.8 g of calcium hydroxide were changed.

The contents of lysine, Mg, P and Ca in this crystal were 13.8%, 18.3%, 18.4% and 2.3%, respectively, and the moisture was 11.5%. In addition, the elution of the crystals in seawater, pure water, and aquatic digestive system equivalents was 5%, 3%, and 100%, respectively.

Example 28

47.7 g of dry crystals (final complex salt) were obtained as in Example 26, except that 2.6 g of tripolyphosphoric acid and 13.3 g of calcium hydroxide were changed.

The contents of lysine, Mg, P and Ca in this crystal were 9.8%, 13.5%, 13.6% and 12.9%, respectively, and the moisture content was 13.7%. In addition, the elution of the crystals in the equivalents of seawater, pure water, and aquatic digestive systems was 4%, 3%, and 100%, respectively.

Example 29

23 g of dry crystals (final complex salt) were obtained as in Example 26 except that 1.0 g of tripolyphosphoric acid and 4.4 g of calcium hydroxide were changed.

The lysine content in this crystal was 13.5%. In addition, the elution of the crystals in the equivalents of seawater, pure water, and aquatic digestive organs was 4%, 2%, and 100%, respectively.

Example 30

47.1 g of tripolyphosphoric acid was dissolved in 500 ml of water, and 63.4 g of calcium hydroxide was added thereto, followed by stirring at room temperature for 1 hour. The slurry thus obtained was suction filtered to separate crystals, and the separated crystals were sufficiently washed with water. The wet crystals were dried to give 96.6 g of tripolyphosphate calcium salt. Instead of tripolyphosphoric acid and calcium hydroxide in Example 26, 49.5 g of crystals (final complex salt) were obtained as in Example 26 except that 15.7 g of tripolyphosphate calcium salt was used.

The elution of these crystals in the equivalents of seawater, pure water, and aquatic digestive systems was 3%, 2%, and 100%, respectively.

Example 31

3.0 g of sodium tripolyphosphate was dissolved in 450 ml of water, and 45 g of Mg salt and 5.0 g of calcium hydroxide obtained in Example 25 were added thereto in order, followed by stirring at room temperature for 2 hours. The obtained reaction slurry was suction filtered and the separated crystals were filtered through 200 ml of water. The obtained wet crystals were dried to obtain 37.8 g of dry crystals (final complex salt).

The contents of lysine, Mg, P, and Ca in the present crystal were 14.3%, 16.1%, 15.6%, and 5.1%, respectively, and the water content was 9.7%. In addition, the elution of the crystals in the equivalents of seawater, pure water, and aquatic animal digestive organs was 3%, 1%, and 100%, respectively.

Example 32

46.4 g of dry crystals (final complex salt) were obtained as in Example 31 except that 3.0 g of sodium hexametaphosphate was used instead of sodium tripolyphosphate.

The contents of lysine, Mg, P and Ca in the present crystal were 13.7%, 16.1%, 16.1% and 5.1%, respectively, and the water content was 10.8%. In addition, the elution of the crystals in seawater, pure water and digestive organ equivalents was 2%, 2% and 100%, respectively.

Example 33

45.8 g of dry crystals (final complex salt) were obtained as in Example 31 except that 3.0 g of metaphosphate was used instead of sodium tripolyphosphate.

The contents of lysine, Mg, P, and Ca in the present crystal were 13.8%, 16.0%, 16.4%, and 5.1%, respectively, and the water content was 10.8%. In addition, the elution of the crystals in seawater, pure water, and aquatic digestive system equivalents was 2%, 2%, and 100%, respectively.

Example 34

19.5 Kg of the slurry obtained in Example 25 was introduced into a 30 L vessel and stirred at 55 ° C. under heating. To this was added simultaneously a dispersion obtained by dispersing 50.48 Kg of 50% lysine aqueous solution and 27.72 Kg of magnesium hydroxide in 155.5 L of water and 42.22 Kg of 85% phosphate. In the meantime, the rate of addition of both the lysine / magnesium hydroxide dispersion and phosphoric acid was adjusted to maintain the pH of the slurry at 8.3. Moreover, the slurry of the same amount and the same amount was taken out from the container, and the liquid amount in the container was kept constant. This operation yielded a total of 265.8 Kg (medium complex salt) slurry.

22.15 Kg of this slurry was stirred at 55 degreeC, The aqueous solution which 0.9 Kg of pyrophosphoric acid was dissolved in 8.4 L of water, and the dispersion liquid which disperse 1.22 Kg of calcium hydroxide in 8.1 L of water were added simultaneously over 2 hours. In the meantime, the pH of the slurry was kept at 9.3. The resulting slurry was vibrated and the separated crystals were washed with 42 L of water. The obtained wet crystals were dried in an air stream at 90 ° C. to obtain 6.86 Kg of dry crystals (final complex salt).

The contents of lysine, Mg, P and Ca in the present crystal were 11.0%, 13.4%, 16.1% and 7.8%, respectively, and the water content was 9.2%. In 60 L of the mother liquor, lysine was present in 1.05 Kg, but Mg, P, and Ca were extremely small, and 99.9% or more was contained in the crystal (final complex salt). In addition, the elution of the crystals in seawater, pure water, and aquatic digestive system equivalents was 2%, 2%, and 100%, respectively.

Example 35

1.95 Kg of the slurry obtained in Example 25 was introduced into a 3 L vessel and stirred at 55 ° C. under heating. To this, a dispersion obtained by dispersing 5.05 Kg of 50% lysine aqueous solution and 2.77 Kg of magnesium hydroxide in 15.6 L of water and 4.22 Kg of 85% phosphate was simultaneously added over 15 hours. In the meantime, the rate of addition of both the lysine / magnesium hydroxide dispersion and phosphoric acid was adjusted to maintain the pH of the slurry at 8.3. Moreover, the amount of liquid in the container was kept constant by taking out the slurry of the same amount and the same amount from the container. This operation yielded a total of 26.6 Kg (of intermediate complex salt) slurry.

22.2 Kg of this slurry was stirred at 55 ° C, and a dispersion obtained by dispersing 9.5 Kg of 10% aqueous phosphoric acid solution and 1.11 Kg of calcium hydroxide in 8 L of water was simultaneously added over 2 hours. In the meantime, the pH of the slurry was kept at 9.3. The obtained slurry was vibrated and the separated crystals were washed with 40 L of water. The obtained wet crystals were dried with an air stream of 90 ° C. to obtain 6.84 Kg of dry crystals (final complex salt).

The contents of lysine, Mg, P, and Ca in the present crystal were 11.0%, 13.4%, 16.2%, and 7.8%, respectively, and the water content was 9.1%. In addition, lysine was present in 1.05 Kg in 60 L of the mother wash liquid, but Mg, P, and Ca were extremely small, and 99.9% or more was contained in the crystal (final complex salt). In addition, the elution of the crystals in seawater, pure water, and aquatic digestive system equivalents was 2%, 2%, and 100%, respectively.

Example 36 (Feed Additive (3) for Aquatic Animal Breeding).

200 g of the dry polyvalent metal complex salt (final complex salt) obtained in Example 34 were weighed, and this was kneaded with 130 g of a 2% aqueous carboxymethylcellulose aqueous solution, followed by extrusion using a disk pelletizer having a diameter of 1.5 mm and a length of about Finely cut to 2 mm, dried, molded into granules with a particle diameter of about 1.5 mm, and dried.

The obtained granules were tested for their elutability in seawater and the equivalents of aquatic animal digestive organs. As a result, the solubilities in seawater were 1% and that of the equivalents of aquatic animal digestive organs was 95%.

Example 37 (aquatic animal feed additive (4)).

200 g of the dry polyvalent metal complex salt (final complex salt) obtained in Example 34 was weighed, 15 g of methionine powder, 40 g of calcium carbonate, 20 g of casein sodium and 4 g of sodium starch glycolate were mixed and kneaded by adding 80 ml of water, It was extruded using a disk pelletizer having a diameter of 1.5 mm, chopped to about 2 millimeters in length, dried, molded into granules having a particle diameter of about 1.5 mm, and dried.

The obtained granules were tested for elution in seawater and the equivalents of aquatic digestive organs of aquatic animals. As for lysine, elution in seawater was 1%, and elution in aquatic equivalents of aquatic animals was 95%. For methionine it was 36% and 98%, respectively.

Example 38

7.0 g of tripolyphosphoric acid was dissolved in 500 ml of water, 40 g of the Mg salt of Example 25 and 6.0 g of aluminum hydroxide were sequentially added thereto, stirred at room temperature for 1 hour, and then filtered by suction, and crystals were separated. The obtained wet crystals were dried under reduced pressure at 65 ° C. to obtain 40.5 g of crystals (final complex salt).

According to the present invention, a complex salt insoluble in neutral to alkaline water and soluble in acidic water, which can be easily prepared from basic amino acids, alkaline earth metals (and divalent or trivalent polyvalent metals other than magnesium) and phosphoric acid. It contains basic amino acids such as lysine and other biologically active substances which are likely to be insufficient in aquatic animal feed, and has excellent protection in water and elution in digestive organs of aquatic animals, It is easy to obtain a feed additive composition for aquatic animal breeding which can be prepared in a form. The feed additive composition for aquatic animal breeding in the form of a homogeneous granule is less susceptible to granule destruction by mixed granulation with other feed ingredients, and compared with the prior art, in the protection of the water and in the digestive organs of aquatic animals. It has an excellent effect of elutability.

The present invention provides a feed additive composition which enables the biologically active substance to be effectively absorbed by aquatic animals, and has a great industrial significance.

Claims (3)

A feed additive composition for aquatic animal breeding, comprising a phosphoric acid amino acid polyvalent metal complex salt of Formula 4 as an active ingredient. Formula 4: R _a M _b H _c H _d PO ₄ ㆍ nH ₂ O Wherein R is a basic amino acid hydrogen cation, M is a polyvalent metal having a valence m other than magnesium, where m is 2 or 3 as the valence of the polyvalent metal. a is 0.05 to 1.0, b is 0.85 to 1.43, c is 0.02 to 0.6, d is 0 to 0.3, a + 2b + cxm + d = 3, n is 0 to 20. A feed additive composition for aquatic animal breeding, comprising a phosphoric acid amino acid polyvalent metal complex salt of Formula 5 as an active ingredient. Formula 5: R _a M _b H _c H _d PO ₄ (PO ₃ ) _m ㆍ nH ₂ O Wherein R is a basic amino acid hydrogen cation, M is a polyvalent metal of valence q other than magnesium, where q is 2 or 3, a is 0.05 to 0.4, b is 0.90 to 1.47, c is 0.01 to 1.4, d is 0 to 0.3, m is 0 a + 2xb + qxc + d = m + 3 n is from 0 to 10. The feed additive for aquatic animal breeding according to claim 1 or 2, characterized in that the divalent or trivalent polyvalent metal other than magnesium in the formula (4) or (5) is at least one kind selected from calcium, aluminum, zinc and iron. Composition.