Ruminant feed additive compositon containing novel phosphoric acid-amino acid- polyvalent metal composite salt

Abstract: Discolsed herein is a ruminant feed additive composition in the form of a powder or granules which comprises as active ingredients a gastric antacid and optionally a water-insoluble salt of a polyvalent metal-sensitive, water-soluble high-molecular substance together with a phosphoric acid-amino acid-polyvalent metal composite salt composed of a phosphoric acid such as orthophosphoric acid, a polyphosphoric acid or a metaphosphoric acid, a basic amino acid such as lysine or methionine, an alkaline earth metal such as calcium or magnesium and, optionally a polyvalent metal such as aluminium. Also is disclosed a method of feeding a ruminant with above-mentioned phosphoric acid-amino acid-polyvalent metal composite salt and a gastric antacid.

Description: The present invention relates to a ruminant feed additive composition and/or a method of administering a feed additive composition to a ruminant. More specifically, the present invention relates to a powdery or uniform granular ruminant feed additive composition which is stable in a rumen of a ruminant and which can release a basic amino acid in an abomasum and lower digestive organs and/or a method of administering this feed additive composition to a ruminant. When biologically active substances such as amino acids, vitamins and the like are orally administered directly into ruminants such as cow, sheep and the like, most of these substances are decomposed with microorganisms in the rumen, and are, therefore, not utilized effectively. Accordingly, rumen by-pass preparations for use in the ruminants by which these biologically active substances are protected from the decomposition with microorganisms in the rumen but are digested and absorbed in the abomasum and lower digestive organs are important in the field of ruminant feed, nutrients, chemicals and the like. With respect to ruminant feed additives containing a biologically active substance, a method in which a biologically active substance is dispersed in a matrix formed of a hydrophobic substance such as fats and oils or a protective substance such as a basic high-molecular substance, and the dispersion is granulated, or a method in which a core containing a biologically active substance is coated with a hydrophobic substance such as fats and oil or an acid-sensitive substance such as a basic high-molecular substance has been proposed so far. Concerning the method in which the biologically active substance is dispersed in the protective substance, for example, Japanese Laid-Open Patent Application (Kokai) [hereinafter referred to as "Japanese Kokai"] No. 168,351/1985 proposes a method which comprises mixing a biologically active substance with at least 20% by weight of calcium carbonate and at least 10% by weight of an aliphatic monocarboxylic acid having 14 or more carbon atoms, hardened fats and oils or the like, and pulverizing the mixture. Japanese Patent Publication No. 10,780/1984 proposes a method which comprises dispersing from 30 to 50% by weight of a biologically active substance in a protective substance comprising from 10 to 35% by weight of a salt of an aliphatic monocarboxylic acid having from 14 to 22 carbon atoms or ricinoleic acid and the remainder of an aliphatic monocarboxylic acid having from 14 to 22 carbon atoms, ricinoleic acid or hardened fats and oils. Concerning the method in which the biologically active substance is coated with the hydrophobic protective substance, for example, Japanese Kokai No. 317,053/1988 proposes a method in which a biologically active substance is coated with a protective agent composed of an aliphatic monocarboxylic acid having from 12 to 24 carbon atoms, hardened fats and oils, lecithin and a glycerin fatty acid ester. Concerning the method in which the biologically active substance is coated with the acid-sensitive protective substance, for example, Japanese Kokai No. 46,823/1979 proposes a method in which a biologically active substance is coated with a coating composition containing a film-forming basic high-molecular substance. Japanese Kokai No. 217,625/1992 proposes a method in which a biologically active substance is spray-coated with casein in the form of an aqueous emulsion or an aqueous dispersion. However, in the method in which the biologically active substance is dispersed into the protective substance, the biologically active substance is present near surfaces of particles. Accordingly, when the protection is taken seriously, the content of the biologically active substance has to be notably decreased. Since the residence time of the water-soluble biologically active substance in the rumen is between 10-odd hours and several days, this biologically active substance can hardly be protected sufficiently. Further, the method in which the biologically active substance-containing core is coated with the acid-sensitive high-molecular substance or the hydrophobic protective substance has been also proposed. However, in view of production of a formula feed which has been increasingly conducted in recent years, mechanical granulation and/or coating destruction occurs owing to mixing or pulverization with another feed composition, and a stability in a rumen of a ruminant is impaired in many cases. Thus, the composition is not said to be a multi-purpose feed additive composition. Thus, it is advisable that a feed additive which can withstand mixing or pulverization with another feed composition take itself the form of a powder or uniform granules and prevent release of a biologically active substance in the rumen and allow elution of the biologically active substance in the abomasum and lower digestive organs. However, when the basic amino acid is used to improve nutrition of the feed, a substance which is composed of a basic amino-acid-containing composition, which takes the form of a powder or uniform granules and which is neutral, insoluble and acid-soluble is only phosphorus wolframate. Japanese Kokai No. 98,357/1988 discloses a ruminant feed additive composition in which a salt of a basic amino acid and an acidic phosphate is coated. In this document, the salt of the acidic phosphoric acid alkaline-earth-metal salt and the basic amino acid corresponds to an analogue of the phosphoric acid-amino acid composite salt of the present invention. However, in the salt of the acidic phosphoric acid alkaline-earth-metal salt and the basic amino acid, the molar ratio of phosphoric acid, alkaline-earth metal and basic amino acid is 1:0.5:1 to 2 which is different from that of the composite salt of phosphoric acid, alkaline-earth metal and basic amino acid in the present invention. The salt of the acidic phosphoric acid alkaline-earth-metal salt and the basic amino acid in the present invention is decomposed in water over the course of time to form an alkaline-earth-metal secondary phosphate, a basic amino-acid primary phosphate or a basic amino-acid secondary phosphate. Since the basic amino-acid phosphate exhibits quite a high water-solubility, this salt is substantially neutral and water-soluble in view of the solubility of the basic amino acid. Phosphoric acid is formed into various salts with alkaline-earth metals, and some of them are insoluble in neutral or alkaline water and are soluble in acidic water. For example, it is known that calcium secondary phosphate, magnesium tertiary phosphate and the like are accumulated as scales in an equipment of fermentation industrial plants in which phosphoric acid is often used, causing troubles in the equipment. Ammonium magnesium phosphate shows the similar nature. With respect to a composite salt comprising 1 mol of phosphoric acid, 1 mol of an alkaline-earth metal and 1 mol of a basic amino acid in which an ammonium ion is replaced with an equivalent basic amino acid as a basic ion, an alkaline-earth-metal salt of a tertiary phosphoric acid salt and/or a secondary phosphoric acid salt comprising 1 mol of phosphoric acid, from 1 to 1.45 mols of an alkaline-earth metal and from 1 to 0.05 mols of a basic amino acid, and a phosphoric acid-amino acid composite salt which is an alkaline-earth-metal salt of condensed phosphoric acid or metaphosphoric acid in which the equivalent ratio of the basic amino acid to the alkaline-earth metal is 0.02 to 0.3:0.7 to 0.98, only a composite salt disclosed in a prior application (Japanese Patent Application No. 306,385/1994) of the present inventors is known. It is an object of the present invention to provide, in consideration of safety and economics, a composition which contains a basic amino acid and which is not dissolved in a rumen of a ruminant but allows elution of the basic amino acid in an abomasum and lower digestive organs and digestion and absorption of the same therein at good efficiency, as well as a method of forming a composition into a powder or granules, and a method of effectively administering the composition into a ruminant. The present inventors have assiduously conducted investigations to achieve the above object, and have consequently found that a composite salt comprising a basic amino acid, an alkaline-earth metal and phosphoric acid is insoluble in neutral or alkaline water and soluble in acidic water, and takes the granular form, that a composite salt (hereinafter referred to as "a polyvalent-metal-treated composite salt") obtained by treating the composite salt comprising the basic amino acid, magnesium and orthophosphoric acid (hereinafter referred to as "an intermediate starting composite salt") with another divalent or trivalent (polyvalent) metal exhibits a better stability to neutral or slightly acidic water, and that the co-existence of the polyvalent-metal-treated composite salt and a water-insoluble salt of a polyvalent-metal-sensitive water-soluble high-molecular substance can further improve a stability to neutral or slightly acidic water. Moreover, it has been found that when orally administering the intermediate starting composite salt, the polyvalent-metal-treated composite salt and/or the composition of the polyvalent-metal-treated composite salt and the water-insoluble salt of the polyvalent-metal-sensitive water-soluble high-molecular substance to a ruminant, a gastric antacid is caused to exist in the composite salts and/or the composition, whereby the composite salts and/or the composition exhibits quite an excellent insolubility in the rumen of the ruminant and an elution property in the abomasum and lower digestive organs. These findings have led to the completion of the present invention. That is, the present invention is to provide a ruminant feed additive composition containing a phosphoric acid-amino acid composite salt of a basic amino acid, an alkaline-earth metal and orthophosphoric acid, represented by formula (1) R a M b H c PO 4 ·nH 2 O wherein R represents a basic amino-acid hydrogen cation, M represents an alkaline-earth metal, a is between 0.05 and 1, b is between 1 and 1.47, c is between 0 and 0.3, a + 2 x b + c = 3, and n is between 0 and 10 and/or a phosphoric acid-amino acid composite salt of a basic amino acid, an alkaline-earth metal and polyphosphoric acid, represented by formula (2) R a M b H c PO 4 (PO 3 ) m ·nH 2 O wherein R represents a basic amino-acid hydrogen cation, M represents an alkaline-earth metal, a is between 0.02 x (m + 3) and 0.3 x (m + 3), b is between 0.35 x (m + 3) and 0.49 x (m + 3), c is between 0 and 0.2 x (m + 3), a + 2 x b + c = m + 3, m is between 1 and 20, and n is between 0 and 10 and/or a phosphoric acid-amino acid composite salt of a basic amino acid, an alkaline-earth metal and metaphosphoric acid, represented by formula (3) R a M b H c (PO 3 ) m ·nH 2 O wherein R represents a basic amino-acid hydrogen cation, M represents an alkaline-earth metal, a is between 0.02 x m and 0.3 x m, b is between 0.35 x m and 0.49 x m, c is between 0 and 0.2 x m, a + 2 x b + c = m, m is between 3 and 50, and n is between 0 and 20 and/or a phosphoric acid-amino acid composite salt of a basic amino acid, magnesium, a polyvalent metal other than magnesium and orthophosphoric ; acid, represented by formula (4) R a Mg b M c H d PO 4 ·nH 2 O wherein R represents a basic amino-acid hydrogen cation, M represents a polyvalent metal of m-valence other than magnesium, m is 2 or 3, a is between 0.05 and 1.0, b is between 0.85 and 1.43, c is between 0.02 and 0.6, d is between 0 and 0.3, a + b x 2 + c x m + d = 3, and n is between 0 and 20 and/or the phosphoric acid-amino acid composite salt of formula (4) and a water-insoluble salt of a polyvalent-metal-sensitive water-soluble high-molecular substance as main components; a powdery or granular ruminant feed additive composition comprising the composite salt and/or the composition and a gastric antacid which is used to make the composite salt and/or the composition quite insoluble in a rumen of a ruminant when orally administering the composite salt and/or the composition to the ruminant but to elute the same in the abomasum and lower digestive organs thereof; and a method of administering the feed additive composition into a ruminant, wherein the gastric antacid is orally administered previously or simultaneously. The present invention is described in detail below. In the present invention, examples of phosphoric acid include orthophosphoric : acid; polyphosphoric acids such as diphosphoric acid (pyrophosphoric acid); polyphosphoric acids such as tripolyphosphoric acid, tetrapolyphosphoric acid and the like; metaphosphoric acids such as trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid and the like; strong phosphoric acid. Salts of orthophosphoric acid, diphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, trimetaphosphoric acid and hexametaphosphoric acid and other metaphosphoric acids are especially preferable in view of the solubility. In the present invention, the basic amino acid includes natural basic amino acids such as lysine, arginine and ornithine; basic derivatives thereof; and basic derivatives of neutral amino acids. These amino acids are used either singly or in combination. Specific examples thereof include natural basic amino acids such as lysine, arginine and ornithine; amides and esters of amino acids such as methionine, tryptophane and threonine; and basic derivatives such as basic amino-acid-containing peptides. In the present invention, examples of the alkaline-earth metals include magnesium, calcium, strontium and barium. Salts of magnesium and calcium are preferable because these are received biologically safely. The phosphoric acid-amino acid composite salt of the present invention is a composite salt which is obtained as a crystalline precipitate when the basic amino acid, the alkaline-earth metal and the phosphoric acid are present in an aqueous solution in a neutral or alkaline condition in which the basic amino acid is used at a relatively high concentration. The phosphoric acid-amino acid composite salt is roughly grouped in 4 types depending on the presence or absence of condensation of phosphoric acid, the mode of condensation and the equivalent ratio of the basic amino acid and the alkaline-earth metal in the case of orthophosphoric acid. The present invention also includes a composite salt of the fifth type wherein the phosphoric acid-amino acid composite salt in which the phosphoric acid is orthophosphoric acid and the alkaline-earth metal is magnesium is treated with the divalent or trivalent (polyvalent) metal other than magnesium to contain the polyvalent metal, and a composition comprising the polyvalent-metal-treated composite salt of the fifth type and a water-insoluble salt of a polyvalent-metal-sensitive water-soluble high-molecular substance. In the present invention, the composite salt of the first type constituting the feed additive composition is an amino-acid composite salt of formula (1) in which the amount of orthophosphoric acid is 3 equivalents, that of the basic amino-acid hydrogen cation (a) is 1 equivalent, that of the alkaline-earth metal (b) is 2 equivalents and that of the acid residue (c) is 0. n is 0, 1 or 2. However, n is between 0 and 10 depending on drying conditions. The composite salt of the second type is a phosphoric acid-amino acid composite salt of formula (1) in which the amount of orthophosphoric acid is 3.0 equivalents, that of the basic amino-acid hydrogen cation (a) is between 0.05 and 1.0 equivalent, that of the alkaline-earth metal (b) is between 2.0 and 2.94 equivalents, that of the acid residue (c) is between 0 and 0.3, a + 2 x b + c is 3 equivalents, and n is between 0 and 10. Preferable is a phosphoric acid-amino acid composite salt in which the amount of orthophosphoric acid is 3.0 equivalents, that of the basic amino-acid hydrogen cation (a) is between 0.05 and 0.8 equivalents, and that of the alkaline-earth metal (b) is between 2.2 and 2.94 equivalents. In the composite salts of the first and second types, magnesium and calcium salts are preferable as an alkaline-earth-metal salt. A salt of magnesium alone and a mixed salt of magnesium and calcium are more preferable. The composite salt of the third type is a phosphoric acid-amino-acid composite salt of formula (2) in which the amount of polyphosphoric acid is 100 equivalents, that of the basic amino-acid hydrogen cation (a) is between 2 and 30 equivalents, that of the alkaline-earth metal (b) is between 70 and 98 equivalents, that of the acid residue (c) is between 0 and 20 equivalents, a + 2 x b + c = 100, and n is between 0 and 10. The composite salt of the fourth type is a composite salt of formula (3) in which the amount of metaphosphoric acid is 100 equivalents, that of the basic amino-acid hydrogen cation (a) is between 2 and 30 equivalents, that of the alkaline-earth metal (b) is between 70 and 98 equivalents, that of the acid residue (c) is between 0 and 20 equivalents, a + 2 x b + c = 100, and n is between 0 and 20. In the composite salts of the third and fourth types, magnesium and calcium salts are preferably used as an alkaline-earth-metal salt. A salt of calcium alone and a mixed salt of magnesium and calcium are more preferable. The composite salt of the fifth type is a phosphoric acid-amino acid composite salt of formula (4) containing the phosphoric acid-amino acid composite salt of formula (1) in which the alkaline-earth metal is magnesium, and a divalent or trivalent (polyvalent) metal other than magnesium. That is, it is a composite salt in which a part of a mixture of a basic amino acid, magnesium and an acid residue is replaced with a polyvalent metal other than magnesium, and which is obtained by using a phosphoric acid-amino acid composite salt comprising orthophosphoric acid, a basic amino acid and magnesium as an intermediate starting composite salt and treating the intermediate starting composite salt with a polyvalent metal other than magnesium. Specifically, it is a salt corresponding to a salt containing a tertiary phosphorate of orthophosphoric acid and/or the tertiary phosphate as a main component and a secondary phosphate in which the amount of phosphoric acid is 3 equivalents, that of the basic amino acid (a) is between 0.05 and 1, that of magnesium (b) is between 1.7 and 2.86, that of a divalent or trivalent [polyvalent (m)] metal (c) other than magnesium is between 0.02 and 0.6 equivalents, that of the acid residue (d) is between 0 and 0.3 equivalents, a + b x 2 + c x m + d = 3, a molar ratio of a secondary phosphate is 1/2 or less of that of a tertiary phosphate, and a water content in the composite salt is 30% or less. Examples of the divalent or trivalent (polyvalent) metal other than magnesium, constituting the phosphoric acid-amino acid composite salt of the fifth type include alkaline-earth metals such as calcium, strontium and barium; transition metals such as aluminum, iron, cobalt, manganese and chromium; and divalent metals such as zinc and cadmium. Calcium, aluminum, iron and zinc salts are preferably used since these are received biologically safely. The composition comprising the polyvalent-metal-treated composite salt of the fifth type and the water-insoluble salt of the polyvalent-metal-sensitive water-soluble high-molecular substance is obtained by causing the composite salt of the fifth type and the polyvalent-metal-sensitive water-soluble high-molecular substance to exist in water. With respect to the polyvalent-metal-sensitive, water-soluble high-molecular substance in the present invention, the term "polyvalent-metal-sensitive" means that the water-soluble high-molecular substance or its water-soluble salt is mixed with the polyvalent-metal-containing aqueous solution to form a salt which has a markedly increased viscosity, which gels or which is insoluble in water. The water-insoluble salt of the polyvalent-metal-sensitive water-soluble high-molecular substance which forms the ruminant feed additive composition in combination with the phosphoric acid-amino acid composite salt in the present invention is not particularly limited so long as it is remarkably viscous, gels or is insoluble in water by the reaction with the polyvalent metal. This salt includes water-insoluble salts of polysaccharides having a carboxyl group, synthetic high-molecular substances and proteins. Examples of the polysaccharides having the carboxyl group include alginic acid, dieran gum, pectin, carboxymethyl cellulose and carboxymethyl starch. Examples of the high-molecular substances include polyacrylic acid and/or a copolymer of polyacrylic acid, and polymethacrylic acid and/or a copolymer of polymethacrylic acid. Examples of the proteins include soybean protein and casein. As the polyvalent metal salt, a calcium salt, an aluminum salt, a zinc salt and an iron salt are especially preferable. A process for producing the phosphoric acid-amino acid composite salt of the first or second type is not particularly limited so long as the salt is insoluble in a neutral or alkaline aqueous solution and is soluble in an acidic aqueous solution. Roughly, the following four processes are preferable. In the first process, a secondary phosphate of an alkaline-earth metal is dispersed into a large amount of a basic aqueous solution of a basic amino acid, the dispersion is heated, and the precipitate obtained is washed. Specifically, a process is mentioned in which an alkaline-earth-metal secondary phosphate such as magnesium hydrogenphosphate or calcium hydrogenphosphate is added to a large amount of a basic concentrated aqueous solution of a basic amino acid formed through the treatment with an ion exchange resin, and the mixture is heated and mixed while being stirred. The alkaline-earth-metal secondary phosphate in the mixed solution disappears over the course of time, and the phosphoric acid-amino acid composite salt is formed as a precipitate. When the precipitate is subjected to solid-liquid separation and a large amount of the basic amino acid is then washed with water and dried, the phosphoric acid-amino acid composite salt composition containing the composite salt of the first type as a main component is obtained. In the second process, an aqueous solution of an alkaline-earth metal and orthophosphoric : acid are mixed at an equivalent ratio of 2.9 to 2.0:3.0 in a large amount of a basic aqueous solution of a basic amino acid, and the resulting precipitate is washed. Specifically, 3 equivalents or more of a basic concentrated aqueous solution of a basic amino acid is neutralized with 3 equivalents of orthophosphoric acid to form a tertiary phosphate solution of a high concentration. From 2.9 to 2.0 equivalents of a concentrated aqueous solution of a neutral salt of an alkaline-earth metal such as magnesium chloride or magnesium sulfate are added thereto, and the mixture is stirred. The resulting precipitate is subjected to solid-liquid separation, and a large amount of a basic amino acid is washed with water and dried. In this process, the phosphoric acid-amino acid composite salt composition containing the composite salt of the first or second type as a main component is obtained depending on the addition rate and the type of the seed crystal in the addition. That is, when an alkaline-earth-metal neutral salt solution is gradually added in an amount of approximately 2 equivalents relative to 3 equivalents of orthophosphoric acid using the composite salt of the first type as a seed crystal, the phosphoric acid-amino acid composite salt containing the composite salt of the first type as a main component is obtained. On the contrary, when the alkaline-earth-metal neutral salt solution is rapidly added in an amount of approximately 2.8 equivalents relative to 3.0 equivalents of orthophosphoric acid, the phosphoric acid-amino acid composite salt composition containing the composite salt of the second type as a main component is obtained. In the third process, from 2.9 to 2.0 equivalents of an alkaline-earth-metal hydroxide is added to a solution obtained by mixing and neutralizing 1.0 equivalent of a basic aqueous solution of a basic amino acid with 3.0 equivalents of orthophosphoric acid, and the resulting precipitate is washed. Specifically, 1.0 equivalent of a basic concentrated aqueous solution of a basic amino acid is mixed and neutralized with 3.0 equivalents of orthophosphoric acid to form a concentrated aqueous solution of the basic amino acid primary phosphate, and from 2.9 to 2.0 equivalents of the alkaline-earth-metal hydroxide such as magnesium hydroxide or calcium hydroxide are added to this solution in the form of an aqueous dispersion. The alkaline-earth-metal hydroxide added disappears over the course of time, and the phosphoric acid-amino acid composite salt is formed as a precipitate. The precipitate is subjected to solid-liquid separation, and a large amount of the basic amino acid is then washed with water, and dried to obtain a phosphoric acid-amino acid composite salt containing the composite salt of the secondary type as a main component. In the fourth process, from 2.94 to 2.2 equivalents of an alkaline-earth-metal hydroxide is added to a solution obtained by mixing and neutralizing from 0.05 to 0.8 equivalents of a basic aqueous solution of a basic amino acid with 3.0 equivalents of orthophosphoric acid, and the mixture is then heat-dried. Specifically, from 0.05 to 0.8 equivalents of a basic concentrated aqueous solution of a basic amino acid are mixed and neutralized with 3.0 equivalents of orthophosphoric acid to form a mixed concentrated aqueous solution of a primary phosphate and orthophosphoric acid, and from 2.94 to 2.2 equivalents of an alkaline-earth-metal hydroxide such as magnesium hydroxide or calcium hydroxide are added to this solution in the form of an aqueous dispersion. The alkaline-earth-metal hydroxide added disappears over the course of time, and the phosphoric acid-amino acid composite salt is formed as a precipitate. When the precipitate is dried as it is, the phosphoric acid-amino acid composite salt composition containing the composite salt of the second type as a main component is obtained. In these four processes, the basic concentrated aqueous solution of the basic amino acid is adopted as a starting material, and the amino-acid composite salt is formed by the reaction in which the basic amino acid is used at a relatively high concentration. In the present invention, the concentration of the basic amino acid is preferably between 10 and 60 parts by weight per 100 parts by weight of the total water content present in the reaction system in the case of the second process in which the highest concentration is selected, and it is preferably between 3 and 20 parts by weight per 100 parts by weight of the total water content present in the reaction system in the case of the fourth process in which the lowest concentration is selected. These four processes can also be used in combination as required. Specific examples thereof include a process in which an appropriate amount of a concentrated aqueous solution of orthophosphoric acid and an alkaline-earth-metal neutral salt is added to a reaction solution in which the phosphoric acid-amino acid composite salt is formed as a precipitate in the first process, these are mixed while being stirred, and the mixture is heated, whereby the concentrated aqueous solution is reacted with the large amount of the basic amino acid remaining in the reaction solution; and a process in which an appropriate amount of an alkaline-earth-metal hydroxide is added to a reaction solution in which a phosphoric acid-amino acid composite salt is formed as a precipitate in the second process, whereby the alkaline-earth-metal hydroxide is reacted with the large amounts of the basic amino acid and phosphoric acid remaining in the reaction solution. The thus-obtained phosphoric acid-amino acid composite salt is a mixture of the composite salts of the first and second types, and the process and the reaction conditions influence the composition ratio thereof. The third or fourth process for producing a phosphoric acid-amino acid composite salt in which phosphoric acid is polyphosphoric acid or metaphosphoric acid is not particularly limited so long as it is insoluble in a neutral or alkaline aqueous solution and is soluble in an acidic aqueous solution. It is approximately identical to the process for producing the composite salt of orthophosphoric acid except that phosphoric acid is polyphosphoric acid or metaphosphoric acid. Roughly, the following three processes are preferable. In the first process, from 70 to 130 equivalents, per 100 equivalents of the above-mentioned phosphoric acid, of a neutral aqueous solution of an alkaline-earth metal are added to a basic aqueous solution obtained by adding the above-mentioned phosphoric acid and/or an alkali-metal salt of the above-mentioned phosphoric acid to a large amount of a basic aqueous solution of a basic amino acid, and the resulting precipitate is washed and dried to obtain the composite salt. In the second process, an acidic or neutral aqueous solution obtained by neutralizing a basic aqueous solution of from 2 to 50 equivalents, per 100 equivalents of the above-mentioned phosphoric acid, of a basic amino acid is mixed with from 70 to 130 equivalents of an alkaline-earth-metal hydroxide and/or oxide, and the resulting precipitate is washed and dried to obtain the composite salt. In the third process, an acidic aqueous solution formed by neutralizing a basic aqueous solution containing from 2 to 30 equivalents, per 100 equivalents of the above-mentioned phosphoric acid, of a basic amino acid with 100 equivalents of the above-mentioned phosphoric acid is mixed with from 70 to 130 equivalents of an alkaline-earth-metal hydroxide and/or oxide, and the reaction product is dried as it is to obtain the composite salt composition. The composite salt of the third or fourth type in the present invention may be prepared separately. It is also preferable to prepare the composite salt mixed composition of the third and fourth types by mixing the starting polyphosphoric acid and metaphosphoric acid simultaneously or previously. Besides the process for preparing the composite salts of the first and second types or the composite salts of the third and fourth types separately in the present invention, there is a process for preparing the composite salt mixed composition of the first to fourth types by mixing the starting phosphoric acids simultaneously or previously. Preferable are a process in which condensed phosphoric acid and/or metaphosphoric acid and an alkaline-earth metal are added to a reaction solution in which the composite salt compositions of the first and second types are formed previously to prepare the composite salt of the third and/or fourth type, and a process in which orthophosphoric acid and an alkaline-earth metal are added to a reaction solution in which the composite salt compositions of the third and fourth types are formed previously to prepare the composite salt mixed composition of the first to fourth types. The fifth process for preparing the phosphoric acid-amino acid composite salt in the present invention is not particularly limited so long as it is insoluble in a neutral or alkaline aqueous solution and soluble in an acidic aqueous solution. Preferable is a process in which an intermediate starting composite salt is mixed with a solution of a divalent or trivalent (polyvalent) metal other than magnesium, and the mixture is separated and dried. The intermediate starting composite salt may be prepared by the process for producing the composite salt of the first or second type, provided that the alkaline-earth metal is limited to magnesium. The above-mentioned four processes are preferable. In the present invention, the salt solution of the divalent or trivalent (polyvalent) metal other than magnesium which is used when treating the intermediate starting composite salt is not particularly limited. Preferable is a weakly acidic or basic aqueous solution or dispersion containing at least 0.001 parts by weight, per 100 parts by weight of the solution, of the polyvalent metal ion other than magnesium. Specific examples thereof include aqueous solutions of aluminum salts such as aluminum chloride, polyaluminum chloride, aluminum sulfate, ammonium alum and potassium alum; aqueous solutions or aqueous dispersions of calcium salts such as calcium chloride, calcium sulfate, calcium hydroxide and calcium nitrate; aqueous solutions of iron salts such as ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, potassium iron sulfate and ammonium iron sulfate; and aqueous solutions or aqueous dispersions of zinc salts such as zinc chloride, ammonium zinc chloride and zinc hydroxide. These solutions of the polyvalent metals other than magnesium may be used either singly or in combination as a mixed salt solution or a composite salt solution. The necessary amount of the divalent or trivalent (polyvalent) metal salt other than magnesium, which is used to obtain the polyvalent-metal-treated composite salt in the present invention varies depending on the time of the contact with the intermediate starting composite salt, the concentration of the divalent or trivalent (polyvalent) metal salt other than magnesium and the dispersion concentration of the intermediate starting composite salt in the contact. However, since most of the divalent or trivalent (polyvalent) metal ions other than magnesium migrate into the desired composite salt, the concentration of this metal salt is preferably between 0.02 and 0.6 mols per mol of phosphoric acid in the intermediate starting composite salt. In this invention, a method of forming a composition comprising a polyvalent-metal-treated composite salt and a polyvalent-metal-sensitive water-soluble high-molecular substance is not particularly limited. Preferable are a method in which the composite salt is previously prepared, and is then mixed with an aqueous solution of an alkali-metal salt and/or an ammonium salt of a polyvalent-metal-sensitive water-soluble high-molecular substance, and the mixture is dried; and a method in which an intermediate starting composite salt is mixed with an aqueous solution of an alkali-metal salt and/or an ammonium salt of a polyvalent-metal-sensitive water-soluble high-molecular substance, and the mixture is then brought into contact with a salt solution of a divalent or trivalent (polyvalent) metal other than magnesium, separated and dried. In the present invention, the gastric antacid is not particularly limited so long as it controls the change in the pH of the content of the rumen (hereinafter referred to as "rumen solution") and maintains the pH at from 6.2 to 7.0. Carbonates, hydrogencarbonates, hydroxides and oxides of alkali metals and alkaline-earth metals are preferable because they are non-toxic. Most preferable are sodium carbonate, sodium hydrogencarbonate, magnesium hydroxide, magnesium oxide, potassium hydroxide, calcium carbonate and magnesium carbonate which exhibit an appropriate basicity. These can be used either singly or in combination. The administration of the ruminant feed additive composition containing the phosphoric acid-amino acid composite salt in the presence of the gastric antacid is effective for controlling the change in the pH of the rumen solution and exhibiting in the rumen solution the properties of the phosphoric acid-amino acid composite salt which is insoluble in neutral or alkaline water and soluble in acidic water. That is, it has been observed that the pH of the rumen solution is sometimes decreased to less than 6.2 depending on the feed composition, the physical condition of the ruminant or the change in the pH over the course of time by the fermentation of materials in the rumen. The composition of the phosphoric acid-amino acid composite salt is gradually dissolved in the rumen solution having the low pH to elute the basic amino acid as an active ingredient. Accordingly, maintaining the pH at 6.2 or more results in the increase in the usefulness of the composition of the phosphoric acid-amino acid composite salt in the present invention. In general, the normal pH of the rumen solution of ruminants including a milk cow is between 6.2 and 7.0, and the notable decrease in the pH leads to the abnormal fermentation of the rumen. For example, acetic acid-productive microorganisms are grown more than propionic acid-productive microorganisms, decreasing production of the milk fat which largely depends on propionic acid formed in the rumen. Further, when the low pH level is continued, a physical condition of a milk cow is deteriorated owing to abnormal growth of lactic acid-productive microorganisms, and the milk cow is sometimes dead. In the present invention, a process of forming the ruminant feed additive composition containing the phosphoric acid-amino acid composite salt and/or the phosphoric acid-amino acid composite salt composition and the gastric antacid as active ingredients is not particularly limited. Preferable examples thereof include a method in which powders are mixed to form a mixed powder, a method in which the phosphoric acid-amino acid composite salt and/or the phosphoric acid-amino acid composite salt composition and the gastric antacid are mixed, and the mixture is granulated, and a method in which the gastric antacid is dissolved or dispersed into water, and the phosphoric acid-amino acid composite salt and/or the phosphoric acid-amino acid composite salt composition is dipped in, or coated with, the solution or the dispersion. In the present invention, the mixing ratio of the phosphoric-acid amino acid composite salt composition and the gastric antacid constituting the ruminant feed additive composition varies depending on the type and composition of the gastric antacid, the feeding conditions of the ruminant to which this composition is administered, and the composition of the feed. The amount of the gastric antacid is preferably between 5 and 1,000 parts by weight per 100 parts by weight of the phosphoric acid-amino acid composite salt composition. In another method in which the phosphoric acid-amino acid composite salt and/or the phosphoric acid-amino acid composite salt composition and the gastric antacid are caused to co-exist when this salt and/or composition is orally administered to a ruminant, the gastric antacid is administered to the ruminant before, or simultaneously with, the administration of this composite salt and/or composition containing the gastric antacid alone or in combination with the other feed composition. A method of administering the gastric antacid is not particularly limited. Preferable examples thereof include a method in which a particulate gastric antacid is mixed with the other feed composition, and the mixture is administered, a method in which a composition obtained by previously mixing a gastric antacid with a part of the other feed composition and pulverizing the mixture is administered, and a method in which a powder or an aqueous solution and/or an aqueous dispersion of a gastric antacid is sprayed on the other feed composition, and the mixture is administered. When employing a complete compound fertilizer administration method (a method in which a crude feed such as a silage or a hay, a high-nutrient compound fertilizer and the other feed additive composition are completely mixed in advance and the mixture is administered to a milk cow or the like) which has been widely used in the dairying in recent years, a method in which a powdery or particulate gastric antacid is mixed with the other feed composition and the mixture is administered to an animal, and a method in which a composition obtained by mixing a gastric antacid with a part of the other feed composition in advance and administering the mixture to an animal are preferably used. On the other hand, with respect to the feed additive composition containing the phosphoric acid-amino acid composite salt and/or the phosphoric acid-amino acid composite salt composition as a main component in the present invention, the composite salt composition is dried, and pulverized, and the powder is used as it is, regardless of the use of the gastric antacid. Alternatively, the composition is used as a ruminant feed additive composition in the form of granules which have not been pulverized, or in the form of granules having an appropriate diameter. In the present invention, the granules of the phosphoric acid-amino acid composite salt are uniform granules which are free from a specific structure such as a structure coated with the other coating component or the like. With respect to the uniform granules in the present invention, the composition of granular materials having a diameter of from approximately 1 to 2 mm, which are obtained from the uniform granules, is not changed. That is, the limit of the diameter in which granules are destroyed through chewing is between approximately 1 and 2 mm. Therefore, when the composition of the granular materials having a diameter of from approximately 1 to 2 mm is uniform, the composition of the granules after chewing is constant. Thus, when the granules are mixed or pulverized with the other feed components, the elution of the basic amino-acid component is not greatly changed. The granulation can be conducted by a usual method so long as the above-mentioned uniformity is provided. Preferable are a method in which the composite salt is mixed with an appropriate binder, and the mixture is granulated through extrusion-granulation, rolling-granulation, compression-granulation, melt-spray-granulation or the like, a method in which a slurry is spray-dried, and a method in which a powder is granulated together with an appropriate binder through granulation using a fluidized bed or through stirring-granulation. The binder is not particularly limited, and an ordinary binder can be used. The binder includes water-soluble binders and hydrophobic binders. Specific examples of the water-soluble binders include water-soluble polysaccharides such as a starch, a carboxymethyl cellulose salt, an alginate, hydroxypropyl cellulose and a starch glycolic acid salt; water-soluble proteins such as casein sodium, gelatin and soybean protein; saccharides such as molasses, lactose and dextrin; and synthetic high-molecular substances such as a polymethacrylate salt, polyvinyl alcohol and polyvinyl pyrrolidone. Specific examples of the hydrophobic binders include natural waxes such as a shellac resin, a rosin, a bees wax and a paraffin wax; higher aliphatic acids such as cetanol and stearic acid; materials associated with fats and oils, such as higher fatty acid metal salts, animal and vegetable fats and oils, and hardened animal and vegetable fats and oils; nonionic surfactants such as glycerin monostearate; and semi-synthetic resins and synthetic high-molecular substances such as acetyl cellulose, polyvinyl acetate, ester gum and a coumarone resin. The ratio of the binder to the phosphoric acid-amino acid composite salt which undergoes granulation varies depending on the type of the binder. It is preferably between 0.1 and 50% by weight per 100 parts by weight of the phosphoric acid-amino acid composite salt. Further, the diameter of the granules is not particularly limited. The granules having an average diameter of approximately 5 mm or less is preferable because the irregularity of the feed is decreased. The granules having an average diameter of from 2 to 0.2 mm are especially preferable because they facilitate the mixing with other feed components. The granules containing the phosphoric acid-amino acid composite salt in the present invention can be prepared by adding, besides the amino-acid composite salt and the binder, other additives in order to adjust the specific gravity, to increase the strength of granules, to increase the melt-destruction in the abomasum, to improve processability in preparation of the granules, and so forth. The additives are selected from powders and waxes to form uniform granules. Specific examples thereof include inorganic substances such as carbonates, phosphates and hydroxides of alkaline-earth metals, talc, bentonite, clay and fine silica; and organic substances such as paraffin wax, polyethylene powder, pulp powder, cellulose powder and xanthone. In addition, the granules containing the phosphoric acid-amino acid composite salt in the present invention can be prepared by uniformly dispersing the other biologically active substance unless impairing the protection of the phosphoric acid-amino acid composite salt in the rumen and the elution in the abomasum. The other biologically active substance includes known nutrients and chemicals such as amino acids, derivatives thereof, hydroxy compounds of amino acids, vitamins and veterinary agents. These may be used either singly or in combination. Specific examples thereof include amino acids such as methionine, tryptophan and threonine; amino-acid derivatives such as calcium salts of N-acylamino acid and N-hydroxymethyl methionine; amino-acid hydroxy compounds such as 2-hydroxy-4-methylmercaptobutyric acid and its salt; calory sources such as starch, fatty acid and fatty acid metal salt; vitamins such as vitamin A, vitamin A acetate, vitamin A palmitate, vitamin B group, thiamine, thiamine hydrochloride, riboflavin, nicotinic acid, nicotinic acid amide, calcium panthotenate, choline panthotenate, pyridoxine chloride, choline chloride, cyanocobalamin, biotin, folic acid, p-aminobenzoic acid, vitamin D 2 , vitamin D 3 and vitamin E, as well as substances having the similar properties; tetracycline-type, amino-macrolide-type, macrolide-type and polyether-type antibiotics; insect repellents such as negphon; vermifuges such as piperazine; and hormones such as estrogen, stilbestrol, hexestrol, thyroprotein, goitrogen and growth hormone. The present invention is illustrated more specifically by referring to the following Examples and Comparative Examples. However, the present invention is not limited thereto. With respect to a biologically active substance, an amount of an amino acid and an amount of an amino acid eluted in Examples were measured through liquid chromatography. Elution into a rumen solution A milk cow fitted with a rumen fistula was fed with a usual feed composition. The rumen content was collected from the rune fistula within 1 hour after the administration of the feed. The crude solid material was removed using a gauge to form a rumen solution. Acetic acid was added thereto to adjust the pH to 5.8. Then, the above-mentioned gastric antacid or acetic acid was added thereto to adjust the pH. Two-hundred milliliters of the rumen solution were charged into a 300-milliliter Erlenmeyer flask together with 0.2 g of a sample (The amount of the basic amino acid contained in the sample will be referred to as "M".) and the mixture was shaken at 39°C for 24 hours. After the shaking, the amount (Q) of the basic amino acid eluted in the supernatant of the rumen solution, and the amount (P) of the basic amino acid given after adding 0.6 ml of conc. hydrochloric acid to the rumen solution after the shaking to completely dissolve the remaining sample were analyzed respectively, and the rate (S) of elution of the basic amino acid into the rumen solution was calculated using the following equation. S (%) = [P (mg) - Q (mg)] x 100/M (mg) Elution into a corresponding abomasum solution A sample (approximately 0.5 g) prepared was charged into a 300-milliliter Erlenmeyer flask, and 200 ml of an acetate-phosphate buffer solution corresponding to an abomasum solution were poured therein. The solution was shaken at 39°C for 1 hour. After the completion of the shaking, the amount of the basic amino acid eluted was analyzed, and the rate of elution of the basic amino acid into the abomasum solution was calculated * Acetate-phosphate buffer solution: Buffer prepared by dissolving the following reagents into 1,000 ml of water and adjusting the pH of the solution to 2.2 with hydrochloric acid. sodium dihydrogenphosphate 2-hydrate 1.95 g sodium acetate 3-hydrate 3.40 g Example 1 Magnesium secondary phosphate 3-hydrate (174.3 g) was added to 1,300 g of an L-lysine basic aqueous solution (concentration: 45% by weight), and the mixture was heat-stirred at 80°C for 3 hours. Then, particulate crystals of magnesium secondary phosphate 3-hydrate disappeared, and fine crystals were formed in large amounts. The thus-formed crystals were filtered, washed with 1,000 ml of water, and then dried at 60°C under reduced pressure to obtain 285 g of a white crystalline powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Then, no dissolution was observed therein. This product was designated an intermediate starting composite salt-1. This intermediate starting composite salt-1 (250 g) and 40 g of calcium chloride 2-hydrate were mixed with 2,000 ml of water, and the mixture was stirred at room temperature for 2 hours. After the solid material was separated from the reaction mixture through filtration, 300 ml of water and 3.0 g of carboxymethyl cellulose sodium salt were added thereto. These were mixed well, and the mixture was then dried to give 255 g of desired Composition-1 containing the polyvalent-metal-treated composite salt and carboxymethyl cellulose calcium salt. Example 2 An L-lysine basic aqueous solution (4,386 g, concentration: 20% by weight) was mixed and neutralized with 231 g of phosphoric acid (concentration: 85%). To this mixed solution was added a solution of 493 g of magnesium sulfate 7-hydrate in 1,000 ml of water at a time. The gel-like precipitate formed was filtered, washed with 12,000 ml of water, and then dried at 60°C under reduced pressure to give 280 g of a white powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Consequently, no dissolution was observed therein. This product was designated an intermediate starting composite salt-2. This intermediate starting composite salt-2 (250 g) and 40 g of calcium chloride 2-hydrate were mixed with 2,000 ml of water, and the solution was stirred at room temperature for 2 hours. The solid material was separated from the mixed solution through filtration, and was then dried to obtain 241 g of a desired polyvalent-metal-treated composite salt-2. Example 3 An L-lysine basic aqueous solution (650 g, concentration: 45% by weight) was mixed and neutralized with 461.2 g of phosphoric acid (concentration: 85%). The resulting solution was mixed with a dispersion obtained by fully dispersing 291.7 g of magnesium hydroxide in 1,000 ml of water. Then, the mixture was reacted, and heat-generated to form a white solid material. After this white solid material was heated at 95°C for 3 hours, 3,000 ml of pure water were added thereto, and the mixture was pulverized. The solid material was filtered, washed with 3,000 ml of water, and dried at 60°C under reduced pressure to obtain 750 g of a white powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Consequently, no dissolution was observed therein. This product was designated a composite salt-3. Example 4 An L-lysine basic aqueous solution (311 g, concentration: 47% by weight) was mixed and neutralized with 461.2 g of phosphoric acid (concentration: 85%). The resulting solution was mixed with a dispersion obtained by fully dispersing 291.7 g of magnesium hydroxide in 700 ml of water. Then, the mixture was reacted, and heat-generated to form a white solid material. This white solid material was heated at 90°C for 3 hours, then pulverized, and dried at 60°C under reduced pressure to obtain 750 g of a white powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Consequently, no dissolution was observed therein. This product was designated an intermediate starting composite salt-4. This intermediate starting composite salt-4 (250 g) and 3.0 g of sodium alginate were mixed with 350 ml of water, and the mixture was extruded into a solution of 20 g of calcium chloride in 1,000 ml of water using a syringe. The mixture which was solidified in string form was further dipped therein at room temperature for 2 hours, washed with water, and dried to give 247 g of Composition-4 comprising the polyvalent-metal-treated composite salt and calcium alginate. Example 5 An L-lysine basic aqueous solution (4,386 g, concentration: 20% by weight) was mixed and neutralized with 231 g of phosphoric acid (concentration: 85%), and 20 g of the white crystalline powder obtained in Example 1 were added thereto. When a solution of 407 g of magnesium chloride 6-hydrate in 500 ml of water was gradually added to the solution in small portions, fine crystals were formed. The resulting crystals were filtered, washed with 3 liters of water, and dried at 60°C under reduced pressure to obtain 573 g of a white crystalline powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Consequently, no dissolution was observed therein. This product was designated an intermediate starting composite salt-5. One-hundred grams of this intermediate starting composite salt-5 and 20 g of zinc chloride were mixed with 1,000 ml of water, and the mixture was stirred at room temperature for 3 hours. The solid material was separated from this mixture through filtration, and was then dried to give 103 g of a polyvalent-metal-treated composite salt-5. Example 6 Magnesium secondary phosphate 3-hydrate (87.2 g) was added to 730 g of an L-lysine basic aqueous solution (concentration: 40% by weight), and the mixture was heat-stirred at 80°C for 3 hours. Consequently, particulate crystals of magnesium secondary phosphate 3-hydrate disappeared, and fine crystals were formed. After 46.1 g of phosphoric acid (concentration: 85%) were gradually added to this mixture while being cooled, a solution of 98.6 g of magnesium sulfate 7-hydrate in 150 ml of water was added thereto at a time. Then, the mixture became a viscous crystalline slurry. The resulting crystals were filtered, washed with 1,300 ml of water, and then dried at 60°C under reduced pressure to obtain 198 g of a white crystalline powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Then, no dissolution was observed therein. This product was designated an intermediate starting composite salt-6. One hundred grams of this intermediate starting composite salt-6 and 20 g of zinc chloride were mixed with 1,000 ml of water, and the mixture was stirred at room temperature for 3 hours. After the solid material was separated from the mixture through filtration, 200 ml of water and 3.0 g of pectin were added thereto. These were mixed well, and the mixture was dried to give 100 g of desired Composition-6 comprising the polyvalent-metal-treated composite salt and pectin zinc salt. Example 7 An L-lysine basic aqueous solution (4,873 g, concentration: 30% by weight) was mixed and neutralized with 461 g of phosphoric acid (concentration: 85%). To this mixture was added a solution of 610 g of magnesium chloride 6-hydrate in 1 liter of water at a time. The viscous mixture formed was uniformly mixed with a dispersion obtained by dispersing well 93.3 g of magnesium hydroxide in 700 ml of water, and the resulting mixed solution was allowed to stand overnight to form a white precipitate. The precipitate was filtered, washed with 7,000 ml of water, and then dried at 60°C under reduced pressure to obtain 980 g of a white powder. One gram of this white powder was added to 100 ml of pure water, and the mixture was stirred. Consequently, no dissolution was observed therein. This product was designated an intermediate starting composite salt-7. One-hundred grams of this intermediate starting composite salt-7 and 30 g of aluminum ammonium sulfate (burnt alum) were mixed with 1,000 ml of water, and the mixture was stirred at room temperature for 2 hours. After the solid material was separated from the mixed solution through filtration, 200 ml of water and 2.0 g of sodium polyacrylate were added thereto. These were mixed well, and the mixture was dried to obtain 103 g of desired Composition-7 comprising the polyvalent-metal-treated composite salt and aluminum polyacrylate. Example 8 A milk cow fitted with a rumen fistula was fed with a usual feed composition. The rumen content was collected from the rumen fistula within 1 hour after the administration of the feed. The crude solid material was removed using a gauge to form a rumen solution. Acetic acid was added thereto to adjust the pH to 5.8. Then, sodium carbonate used as a gastric antacid was added thereto to adjust the pH to from 6.8 to 6.2. Acetic acid was added thereto to adjust the pH to 5.5. With respect to Composition-1 comprising the polyvalent-metal-treated composite salt and carboxymethyl cellulose calcium salt, the polyvalent-metal-treated composite salt-2 and the composite salt-3 which were obtained in Examples 1 to 3, the elution into the rumen solution having the pH of from 5.5 to 6.8 and the elution into the corresponding abomasum solution were measured. The results are shown in Table 1. Analysis of amino acid composite salt and composition and elution properties thereof Composition-1 Treated composite salt-2 Composite salt-3 Method Example 1 Example 2 Example 3 Starting materials L-lysine base magnesium secondary phosphate carboxymethylcellulose sodium salt calcium chloride L-lysine base phosphoric acid magnesium sulfate calcium chloride L-lysine base phosphoric acid magnesium hydroxide Main composition Lysine content 46.0% 18.2% 18.5% Mg content 7.4% 14.8% 16.6% Other metal Ca Ca - Its content 2.6% 2.0% Phosphorus content 10.8% 14.9% 15.8 (PO 4 ) (33.1%) (45.7%) (48.5%) Elution into rumen solution pH6.8 67% 10% 44% pH6.5 70% 12% 47% pH6.2 75% 15% 51% pH5.8 85% 25% 65% pH5.5 92% 38% 79% Elution into corresponding abomasum solution 100% 100% 100% Example 9 In the same manner as in Example 8, acetic acid was added to the rumen solution to adjust the pH to 5.8. Then, from 1.2 to 2.5 g, per 200 ml of the rumen solution, of sodium hydrogencarbonate used as a gastric antacid were added to the rumen solution to adjust the pH to from 6.2 to 6.8. With respect to the composite salt-3, Composition-4 comprising the polyvalent-metal-treated composite salt and calcium alginate, the zinc-treated composite salt-5, Composition-6 comprising the polyvalent-metal-treated composite salt and pectin zinc salt and Composition-7 comprising the polyvalent-metal-treated composite salt and aluminum polyacrylate which were obtained in Examples 3 to 7, the elution into the rumen solution having the pH of from 6.2 to 6.8 and the elution into the corresponding abomasum solution were measured. The results are shown in Table 2. Comparative Example 1 With respect to the composite salt-3, Composition-4 comprising the polyvalent-metal-treated composite salt and calcium alginate, the zinc-treated composite salt-5, Composition-6 comprising the polyvalent-metal-treated composite salt and pectin zinc salt and Composition-7 comprising the polyvalent-metal-treated composite salt and aluminum polyacrylate, the elution into the rumen solution having a pH of 5.8 was measured in the same manner as in Example 9. The results are shown in Table 2. Example 10 The calcium-treated composite salt-2, the composite salt-3 and Composition-7 comprising the aluminum-treated composite salt and aluminum polyacrylate which were obtained in Examples 2, 3 and 7 were used as main components in amounts of 10.0. Sodium hydrogencarbonate, magnesium oxide and calcium hydroxide were used as gastric antacids in amounts of 10.0 g, 5.0 g and 7.0 g respectively. Carboxymethyl cellulose sodium salt, potato starch and corn starch were used as binders in amounts of 1.0 g. These components were kneaded with 10 ml of water, formed into strings, dried and cut to form uniform granules having an average diameter of 3 mm. In this manner, Composition Granule-2 comprising the calcium-treated composite salt-2 and the gastric antacid, Composition Granule-3 comprising the composite salt-3 and the gastric antacid and Composition Granule-7 comprising the aluminum-treated composite salt and aluminum polyacrylate were obtained. Two-hundred milligrams of each of the thus-obtained Composition Granules-2, -3 and-7 were charged into 200 ml of a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9. Then, the elution into the rumen solution was measured. The results are shown in Table 3. Comparative Example 2 Ten grams of each of the calcium-treated composite salt-2, the composite salt-3 and Composition-7 comprising the aluminum-treated composite salt and aluminum polyacrylate were added to 10 ml of water together with 1.0 g of carboxymethyl cellulose sodium salt, potato starch or corn starch to form a string-like product. This product was dried, and then cut to form uniform granules having an average diameter of 3 mm. Thus, Composition Granule-2 containing the calcium-treated composite salt-2, Composition Granule-3 containing the composite salt-3, and Composition Granule-7 containing the composition of the aluminum-treated composite salt and aluminum polyacrylate and the gastric antacid were obtained. Two-hundred milligrams of each of the resulting Composition Granules-2, -3 and-5 were charged into 200 ml of a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9. Thus, the elution into the rumen solution was measured. The results are shown in Table 3. Example 11 An L-lysine basic aqueous solution (609 g, concentration: 30% by weight) was mixed and neutralized with 337.9 g of polyphosphoric acid (H 6 P 4 O 13 ) while being cooled. To this solution was added a dispersion of 259.3 g of calcium hydroxide in 500 ml of water. The mixture was heat-generated, and the overall mixture was gradually solidified. The thus-obtained solid material was pulverized, washed with 12,000 ml of water, and then dried at 60°C under reduced pressure to obtain 505.9 g of a white powder. One gram of this white powder was added to 100 ml of pure water and the corresponding abomasum solution, and the mixture was stirred. As a result, no dissolution was observed therein. One gram of this white powder was dissolved in 100 ml of dilute hydrochloric acid, and the concentration of L-lysine was measured. Consequently, it was found to be 165 mg/dl, and the content of L-lysine was 16.5%. Further, 1.00 g of this white powder was mixed with 100 ml of pure water, and the mixture was sonicated for 5 minutes. Then, the concentration of L-lysine in the supernatant was measured, and found to be 18 mg/dl, and the rate of elution into pure water was 11%. The elution of this white powder into the corresponding abomasum solution was evaluated. Then, the rate of elution into the corresponding abomasum solution was 100%. This white powder (0.2 g) and 0.1 g of calcium hydroxide used as a gastric antacid were charged into 200 ml of a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9. Thus, the elution into the rumen solution was measured. The rate of elution into the rumen solution was 12%. Example 12 An L-lysine basic aqueous solution (487 g, concentration: 30% by weight) was mixed with 51.9 g of calcium hydroxide and 216 g of calcium dihydrogen pyrophosphate (CaH 2 P 2 O 7 ), and the mixture was heated at 90°C while being stirred. Then, the overall mixture was gradually solidified. The resulting solid material was pulverized, washed with 10,000 ml of water, and then dried at 60°C under reduced pressure to obtain 356 g of a white powder. One gram of this white powder was added to 100 ml of pure water and the corresponding abomasum solution, and the mixture was stirred. Consequently, no dissolution was observed therein. One gram of this white powder was dissolved in 100 ml of dilute hydrochloric acid, and the concentration of L-lysine was measured. Then, it was found to be 116 mg/dl, and the content of L-lysine was 11.6%. Further, 1.00 g of this white powder was mixed with 100 ml of pure water, and the mixture was sonicated for 5 minutes. The concentration of L-lysine in the supernatant was measured, and found to be 27 mg/dl, and the rate of elution into pure water was 23%. The elution of this white powder into the corresponding abomasum solution was 100%. This white powder (0.2 g) and 0.1 g of sodium hydrogencarbonate used as a gastric antacid were charged into 200 ml of a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9, and the elution into the rumen solution was measured. As a result, the rate of elution into the rumen solution was 25%. Example 13 An L-lysine basic aqueous solution (363 g, concentration: 50% by weight) was mixed and neutralized with 467 g of metaphosphoric acid [(HPO 3 ) n ] while being cooled. To this solution was added a dispersion of 166.7 g of calcium hydroxide in 300 ml of water. The mixture was heat-generated, and the overall mixture was gradually solidified. The thus-obtained solid material was pulverized, washed with 12,000 ml of water, and then dried at 60°C under reduced pressure to obtain 295 g of a white powder. One gram of this white powder was added to 100 ml of pure water and the corresponding abomasum solution, and the mixture was stirred. As a result, no dissolution was observed therein. One gram of this white powder was dissolved in 100 ml of dilute hydrochloric acid, and the concentration of L-lysine was measured. Consequently, it was found to be 99 mg/dl, and the content of L-lysine was 9.9%. Further, 1.00 g of this white powder was mixed with 100 ml of pure water, and the mixture was sonicated for 5 minutes. Then, the concentration of L-lysine in the supernatant was measured, and found to be 2.4 mg/dl, and the rate of elution into pure water was 2.4%. The elution of this white powder into the corresponding abomasum solution was evaluated. Then, the rate of elution into the corresponding abomasum solution was 100%. This white powder (0.2 g) and 0.1 g of magnesium oxide used as a gastric antacid were charged into 200 ml of a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9. Thus, the elution into the rumen solution was measured. The rate of elution into the rumen solution was 15%. Comparative Example 3 The white powder (0.2 g) obtained in each of Examples 11 to 13 was charged into 200 mg of a rumen solution which had been adjusted to a pH of 5.8 as in Example 9, and the elution into the rumen solution was measured. As a result, the rates of elution into the rumen solution were 25%, 37% and 29% respectively. Example 14 L-alginic acid (174.2 g) and 98.0 g of phosphoric acid (concentration: 85%) were dissolved into 300 ml of water, and this solution was mixed with a dispersion obtained by dispersing well 72.9 g of magnesium hydroxide into 200 ml of water. Then, the mixture was reacted, and heat-generated to form a white solid material. After this white solid material was heated at 95°C for 3 hours, 1,000 ml of pure water were added thereto, and the mixture was pulverized, and mixed with 10 g of calcium hydroxide. The mixture was stirred for 2 hours. The solid material was filtered, and washed with 1,000 ml of water. Subsequently, 500 ml of water and 3.0 g of sodium alginate were added thereto. These were mixed well, and dried to obtain 245 g of a desired composition powder comprising the composite salt and calcium alginate. One gram of this powder was added to 100 ml of pure water, and the mixture was stirred. Then, no dissolution was observed therein. One gram of this powder was dissolved in 100 ml of dilute hydrochloric acid, and the concentration of arginine was measured. Then, it was found to be 350 mg/dl, and the content of arginine was 35.0%. Further, 1.00 g of this white powder was mixed with 100 ml of pure water, and the mixture was sonicated for 5 minutes to measure the concentration of arginine in the supernatant. As a result, it was found to be 50 mg/dl, and the rate of elution into pure water was 14.3%. This white powder (0.2 g) and 0.1 g of sodium hydrogencarbonate used as a gastric antacid were charged into 200 ml of a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9, and the elution into the rumen solution was measured. As a result, the rate of elution of arginine into the rumen solution was 16%. Example 15 The intermediate starting composite salt-2 obtained in Example 2 was mixed with 50 g of bentonite, 30 g of casein sodium and 5 g of starch sodium glycolate, and 25 g of magnesium hydroxide used as a gastric antacid and 100 ml of water were added thereto. The mixture was kneaded, extruded using a disc pelletizer having a bore diameter of 2 mm, and cut to a length of approximately 2 mm. The product was dried, and formed into granules having a diameter of approximately 2 mm. The thus-obtained granules were cut into smaller granules having a diameter of approximately 0.5 mm. The five granules thereof were heat-extracted with dilute hydrochloric acid, and the amino-acid content was measured. As a result, no difference in the amino-acid content was observed among these smaller granules The thus-formed granules (0.2 g) were charged into 200 ml of a rumen solution which had been and adjusted to a pH of 5.8 as in Example 9. Thus, the elution into the rumen solution was measured. As a result, the rate of elution into the rumen solution was 5%. The rate of elution of the granules into the corresponding abomasum solution was 97%. With respect to the smaller granules having a diameter of approximately 0.5 mm, the elution into the rumen solution and the elution into the corresponding abomasum solution were evaluated. Consequently, the rate of elution into the rumen solution was 6%, and the rate of elution into the corresponding abomasum solution was 98%. Example 16 Two-hundred grams of Composition-4 comprising the polyvalent-metal-treated composite salt and calcium alginate as obtained in Example 4 were mixed with 15 g of methionine powder, 40 g of calcium carbonate, 20 g of casein sodium and 4 g of carboxymethyl cellulose sodium salt, and 40 g of sodium hydrogenphosphate used as a gastric antacid and 70 ml of water were added thereto. The resulting mixture was kneaded, extruded using a disc pelletizer having a bore diameter of 2 mm, and cut to a length of approximately 2 mm. The product was dried, and formed into granules having a diameter of approximately 2 mm. The thus-obtained granules were cut into smaller granules having a diameter of approximately 0.5 mm. The five granules thereof were heat-extracted with dilute hydrochloric acid, and the amino-acid content was measured. As a result, no difference in the amino-acid content was observed among these smaller granules. The thus-formed granules (0.2 g) were charged into a rumen solution which had been collected and adjusted to a pH of 5.8 as in Example 9. Thus, the elution into the rumen solution was measured. As a result, the rate of elution of lysine into the rumen solution was 10%. At the same time, the elution of methionine into the rumen solution was measured. Consequently, the rate of elution of methionine into the rumen solution was 25%. Further, the elution of the granules into the corresponding abomasum solution was evaluated. The rates of elution of lysine and methionine thereinto were both 98%. With respect to the smaller granules having a diameter of approximately 0.5 mm, the elution into the rumen solution and the elution into the corresponding abomasum solution were evaluated. Consequently, the rate of elution of lysine into the rumen solution was 12%, and the rate of elution of methionine into the rumen solution was 28%. The rates of elution of lysine and methionine into the corresponding abomasum solution were both 99%. Comparative Example 4 Granules were prepared in the same manner as in Examples 15 and 16 except that no gastric antacid was added. Each (0.2 g) of the main components obtained in Examples 15 and 16 was charged into 200 ml of a rumen solution which had been adjusted to a pH of 5.8 as in Example 9, and the elution into the rumen solution was measured. As a result, with respect to the granule composition corresponding to that of Example 15, the rate of elution of lysine into the rumen solution was 25%. With respect to the granule composition corresponding to that of Example 16, the rate of elution of lysine into the rumen solution was 29%, and the rate of elution of methionine into the rumen solution was 39%. Effects of the Invention As stated above, in the present invention, a ruminant feed additive composition which contains a basic amino acid such as lysine or the like that tends to be lacking in a ruminant feed, which is excellent in terms of protection in a rumen and elution in an abomasum can be formed using a composite salt containing a basic amino acid, an alkaline-earth metal and phosphoric acid, a composite salt obtained by treating a composite salt containing a basic amino acid, magnesium and phosphoric acid with a divalent or trivalent (polyvalent) metal other than magnesium, and/or a composition containing the polyvalent-metal-treated composite salt and a water-insoluble salt of a polyvalent-metal-sensitive water-soluble high-molecular substance, and a gastric antacid by which a pH in a rumen can be adjusted to from 6.2 to 7.0. Further, this feed additive composition can effectively be administered to a ruminant by orally administering the gastric antacid before, or simultaneously with, the oral administration of the composite salt and/or the composition of the composite salt as a feed additive composition. The uniform granules in the present invention are less influenced by destruction of the granules owing to chewing or mixing with other feed components. Thus, the present invention can provide a ruminant feed additive composition which is excellent in terms of protection in a rumen and elution in an abomasum in comparison with the prior art. The present invention is to provide a feed additive composition which enables a biologically active substance to be effectively absorbed into a ruminant. Thus, it is extremely significant industrially.

Claims: A ruminant feed additive composition which comprises as active ingredients a gastric antacid and a phosphoric acid-amino acid-polyvalent metal composite salt which is composed of a phosphoric acid, an alkaline-earth metal and a basic amino acid, said phosphoric acid being selected from the group consisting of orthophosphoric acid, polyphosphoric acids, and metaphosphoric acids, and which is insoluble in neutral or alkaline water whereas is soluble in acidic water. The ruminant feed additive composition of Claim 1, wherein said phosphoric acid-amino acid-polyvalent metal composite salt is represented by the following Formula (1), said phosphoric acid being orthophosphoric acid; R a M b H c PO 4 ·nH 2 O wherein R represents a basic amino acid hydrogen cation. M represents an alkaline-earth metal, a is between 0.05 and 1, b is between 1 and 1.47, c is between 0 and 0.3, a + 2 x b + c = 3, and n is between 0 and 10. The ruminant feed additive composition of Claim 1, wherein said phosphoric acid amino acid-polyvalent metal composite salt is represented by the following Formula (2), said phosphoric acid being a polyphosphoric acid selected from the group consisting of pyrophosphoric acid. tripolyphosphoric acid, and tetrapolyphosphoric acid and the like polyphosphoric acid; R a M b H c PO 4 (PO 3 ) m ·nH 2 O wherein R represents a basic amino acid hydrogen cation, M represents an alkaline-earth metal, a is between 0.02 x (m + 3) and 0.3 x (m + 3). b is between 0.35 x (m + 3) and 0.49 x (m + 3), c is between 0 and 0.2 x (m + 3), a + 2 x b + c = m + 3, m is between 1 and 20, and n is between 0 and 10. The ruminant feed additive composition of Claim 1, wherein said phosphoric acid-amino acid-polyvalent metal composite salt is represented by the following Formula (3), said phosphoric acid being a metaphosphoric acid selected from the group consisting of trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid and the like metaphosphoric acids; R a M b H c (PO 3 ) m ·nH 2 O wherein R represents a basic amino acid hydrogen cation, M represents an alkaline-earth metal, a is between 0.02 x m and 0.3 x m, b is between 0.35 x m and 0.49 x m, c is between 0 and 0.2 x m, a + 2 x b + c = m. m is between 3 and 50, and n is between 0 and 20. The ruminant feed additive composition of any one of Claims 1 to 4, wherein said alkaline earth metal is at least one menber selected from the group consisting of magnesium and calcium. A ruminant feed additive composition which comprises as active ingredients a gastric antacid and a phosphoric acid-amino acid-polyvalent metal composite salt represented by the following Formula (4) ; R a Mg b M c H d PO 4 ·nH 2 O wherein R represents a basic amino acid hydrogen cation, M represents a polyvalent metal of m-valence other than magnesium, m is 2 or 3, a is between 0.05 and 1.0, b is between 0.85 and 1.43, c is between 0.02 and 0.6, d is between 0 and 0.3, a + b x 2 + c x m + d = 3, and n is between 0 and 20. A ruminant feed additive composition which comprises as active ingredients a water-insoluble salt of a polyvalent-metal-sensitive, water-soluble high-molecular substance, together with a phosphoric acid-amino acid-polyvalent metal composite salt of Formula (4) above and a gastric antacid. The ruminant feed additive composition of Claim 6 or 7, wherein said divalent or trivalent (polyvalent) metal other than magnesium is at least one member selected from the group consisting of calcium, aluminum, zinc and iron. The ruminant feed additive composition of Claim 7 or 8, wherein said water-insoluble salt of a polyvalent-metal-sensitive, water-soluble high-molecular substance is a water-insoluble salt obtainable by the reaction of a water-soluble salt of a water-soluble high-molecular substance with a polyvalent metal salt, and is at least one member selected from the group consisting of a calcium salt, an aluminum salt, a zinc salt or an iron salt of alginic acid, carrageenan, dieran gum, pectin, carboxymethyl cellulose, carboxymethyl starch, polyacrylic acid, a polyacrylic acid copolymer, polymethacrylic acid, a polymethacrylic acid copolymer, soybean protein or casein. The ruminant feed additive composition of any one of Claims 1-4 and 6-8, wherein said amino acid is at least one member selected from the group consisting of L-lysine and L-arginine. The ruminant feed additive composition of any one of Claims 1-4 and 6-8, wherein said gastric antacid is at least one member selected from the group consisting of sodium carbonate, sodium hydrogencarbonete, magnesium hydroxide, magnesium oxide, potassium hydroxide, calcium carbonate. calcium hydroxide, and magnesium carbonate. The ruminant feed additive composition of any one of Claims 1-4 and 6-8, wherein said ruminant feed additive composition is in the form of a powder or granules. The ruminant feed additive composition of any one of Claims 1-4 and 6-8, which comprises other biologically active substance(s) together with a phosphoric acid-amino acid-polyvalent metal composite salt and a gastric antacid. A method of feeding a ruminant, wherein when a ruminant feed additive composition comprising, as the main component, a phosphoric acid-amino acid-polyvalent metal composite salt as set forth in any one of Claims 1-4, 6 and 10 is administered to the ruminant, a gastric antacid is orally administered previous to or simultaneously with said ruminant feed additive composition. A method of feeding a ruminant, wherein when a ruminant feed additive composition comprising as the main components a phosphoric acid-amino acid-polyvalent metal composite salt of Formula (4) above and a water-insoluble salt of a polyvalent-metal-sensitive, water-soluble high-molecular substance is administered to the ruminant, a gastric antacid is orally administered previous to or simultaneously with said ruminant feed additive composition. The method of Claim 14 or 15, wherein said gastric antacid is at least one member selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium carbonate and magnesium carbonate.

Inventors: IKEDA TORU, KITAMURA NOBUYOSHI, KOBAYASHI HISAMINE, SATO HIROYUKI, YUKAWA TOSHIHIDE, IKEDA, TORU, KITAMURA, NOBUYOSHI, KOBAYASHI, HISAMINE, SATO, HIROYUKI, YUKAWA, TOSHIHIDE, Ikeda, Toru c/o Cen. Res.Lab.,Ajinomoto Co., Inc., Kitamura, Nobuyoshi c/o Cen. Res. Lab.,, Kobayashi, Hisamine c/o Cen. Res. Lab.,, Sato, Hiroyuki c/o Cen. Res. Lab.,, Yukawa, Toshihide c/o Cen. Res.Lab.,Ajinomoto Co.,
Applicants: AJINOMOTO KK, AJINOMOTO CO., INC.
Application year: 1996
Main classification: A23K1
IPC codes: A23K1